CN1659728A

CN1659728A - Alkali/transition metal halo-and hydroxy-phosphates and related electrode active materials

Info

Publication number: CN1659728A
Application number: CN028210190A
Authority: CN
Inventors: J·巴克; M·Y·塞义迪; J·索叶
Original assignee: Valence Technology Inc
Current assignee: Valence Technology Inc
Priority date: 2001-10-26
Filing date: 2002-10-18
Publication date: 2005-08-24
Anticipated expiration: 2022-10-18
Also published as: EP2242134A1; CA2746409A1; KR100989019B1; WO2003038930A3; CN100517817C; CA2746409C; US20040265695A1; KR101121472B1; EP1444744A2; AU2002337911A1; CA2463872A1; CA2463872C; JP4965061B2; KR20050037485A; JP2006516172A; WO2003038930A2; US20070190425A1; WO2003038930A8; KR20100119810A; US20030027049A1

Abstract

Electrode active materials comprising lithium or other alkali metals, a transition metal, a phosphate or similar moiety, and a halogen or hydroxyl moiety. Such electrode actives include those of the formula: AaMb(XY4)cZd, wherein (a) A is selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<a</=6; (b) M comprises one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 1 </= b </= 3; (c) XY4 is selected from the group consisting of X'O4-XY'X, X'O4-yY'2y, X'S4, and mixtures thereof, where X' is P, As, Sb, Si, Ge, S, and mixtures thereof; X'' is P, As, Sb, Si, Ge and mixtures thereof; Y' is halogen; 0</=5 x < 3; and 0 < y < 4; and 0<c</=3; (d) Z is OH, halogen, or mixtures thereof, and 0 < d</= 6; and wherein M, X, Y, Z, a, b, c, d, x and y are selected so as to maintain electroneutrality of said compound. In a preferred embodiment, M comprises two or more transition metals from Groups 4 to 11 of the Periodic Table. In another preferred embodiment, M comprises M'M'', where M' is at least one transition metal from Groups 4 to 11 of the Periodic Table; and M' is at least one element from Groups 2, 3, 12, 13, or 14 of the Periodic Table. Preferred embodiments include those having where c = 1, those where c = 2, and those where c=3. Preferred embodiments include those where a</= 1 and c = 1, those where a = 2 and c = 1, and those where a >/= 3 and c=3. This invention also provides electrodes comprising an electrode active material of this invention, and batteries that comprise a first electrode having an electrode active material of this invention; a second electrode having a compatible active material; and an electrolyte.

Description

Alkali/transition metal halophosphates and hydroxyphosphates and related electrode active materials

This application is a continuation-in-part application filed on 27/4/2000 of U.S. patent application serial No. 09/559,861.

Technical Field

The invention relates to an electrode active material, an electrode and a battery. In particular, the present invention relates to active materials comprising lithium or other alkali metals, transition metals, phosphate or similar moieties, and halogen or hydroxyl moieties.

Background

A wide variety of electrochemical cells or "cells" are known in the art. Generally, a battery is a device that converts chemical energy into electrical energy through an electrochemical oxidation-reduction reaction. Batteries are used in a wide variety of applications, particularly as a source of energy for devices that cannot be physically supplied by a centralized energy supply source (e.g., a commercial power plant using a utility transmission line).

Batteries generally comprise three parts: a negative electrode comprising a material that is oxidized (generates electrons) during discharge of the battery (i.e., when the battery is powered); a positive electrode containing a material that is reduced (accepts electrons) during discharge of the battery; and an electrolyte that provides ions that are transported between the negative electrode and the positive electrode. During discharge, the anode is the negative electrode of the battery and the cathode is the positive electrode. More specifically, the battery may be characterized by the specific materials that make up these three parts. The selection of the materials for these portions enables a battery to be obtained with specific voltage and discharge characteristics that can be optimized for a particular application.

Generally, batteries are classified into: "galvanic cells" in which the electrochemical reaction is substantially irreversible, such that the cell becomes unusable once discharged; "Secondary battery" in which the electrochemical reaction is at least partially reversible, thereby allowing the battery to be "recharged" for more than one use. The use of secondary batteries is increasing in many applications because secondary batteries have advantages of convenience (especially in applications where it is difficult to replace batteries), low cost (by reducing the need to replace batteries), and environmental benefits (by reducing waste batteries).

Various secondary battery systems are known in the art. The most common of these systems are lead-acid, nickel-cadmium, nickel-zinc, nickel-iron, silver oxide, nickel metal hydride, rechargeable zinc-manganese dioxide, zinc-bromide, metal-air and lithium batteries. Systems containing lithium and sodium have many potential benefits because these metals are lightweight, but have a high standard potential. Lithium batteries are particularly attractive commercially for a variety of reasons because of their high energy density, battery voltage and long service life.

Lithium batteries are made from one or more lithium electrochemical cells containing electrochemically active (electroactive) materials. These batteries have a metallic lithium negative electrode and a metal chalcogenide (oxide) positive electrode, commonly referred to as "lithium metal" batteries. The electrolyte typically comprises a salt of lithium dissolved in one or more solvents, typically non-aqueous, aprotic organic solvents. Other electrolytes are solid electrolytes (typically a polymer matrix) that contain an ionically conductive medium (typically a lithium-containing salt dissolved in an organic solvent) and a polymer that may itself be ionically conductive but electrically insulating.

A battery having a metal lithium negative electrode and a metal chalcogenide positive electrode is charged in an initial state. During discharge, the metallic lithium negative electrode supplies electrons to an external circuit. The positively charged ions are generated and pass through the electrolyte into the electrochemically active (electroactive) material of the positive electrode. Electrons from the cathode pass through an external circuit, powering the device, and finally returning to the anode.

Another type of lithium battery uses an "insertion negative electrode" rather than lithium metal and is commonly referred to as a "lithium ion" battery. The insertion electrode comprises a material having a lattice structure into which ions can be inserted and then extracted. The inserted ions do not chemically alter the compound, but rather slightly expand the length of the internal lattice of the compound, without producing significant bond breaks or atomic reorganization. The insertion negative electrode contains, for example, a lithium metal chalcogenide, a lithium metal oxide, or a carbon material such as coke and graphite. These negative electrodes are used with lithium-containing intercalation positive electrodes. In the initial state of such a battery, it is not charged, since the negative electrode does not contain a source of cations. Therefore, prior to use, these batteries must be charged to transport cations (lithium) from the positive electrode to the negative electrode. During discharge, lithium is transported from the negative electrode back to the positive electrode. During a subsequent recharging process, the lithium is transported back to the negative electrode and reinserted there. Such lithium ions (Li) between the negative electrode and the positive electrode in charge-discharge cycles⁺) To make these batteries known as "rocking chair" batteries.

Various materials have been proposed for use as positive active materials in lithium batteries. These materials include, for example, MoS₂、MnO₂、TiS₂、NbSe₃、LiCoO₂、LiNiO₂、LiMn₂O₄、V₆O₁₃、V₂O₅、SO₂、CuCl₂. Transition metal oxides of the formula Li_xMO_yThose indicated are among the preferred materials in batteries with inserted electrodes. Other materials include lithium transition metal phosphates, such as LiFePO₄And Li₃V(PO₄)₃. Materials having a structure similar to olivine or NASICON materials are known in the prior art. Cathode materials known in the art are disclosed in: hossain "Rechargeable lithium battery (ambient temperature)" (Rechargeable)Lithium Batteries (American Temperature)), Battery Handbook (Handbook of Batteries), second edition, Chapter 36, Mc-Graw Hill (1995); U.S. patent 4,194,062 issued to Carides et al at 3/18 1980; U.S. patent 4,464,447 to Lazzari et al issued on 8/7/1984; U.S. Pat. No. 5,028,500 issued to Fong et al, 7, 2, 1991; U.S. Pat. No. 5,130,211 to Wilkinson et al, issued 7, 14.1992; U.S. patent 5,418,090 to Koksbang et al, issued 5, 23, 1995; U.S. patent 5,538,814 to Kamauchi et al, issued on 23/7/1996; U.S. patent 5,695,893 to Arai et al, issued on 9/12/1997; U.S. patent 5,804,335 to Kamauchi et al, issued on 8/9/1998; U.S. Pat. No. 5,871,866 to Barker et al, 2, 16, 1999; U.S. Pat. No. 5,910,382 issued to Goodenough et al, 8/6/1999; PCT publication WO/00/31812 to Barker et al, published in 6/2/2000; PCT publication WO/00/57505 to Barker et al, published in 9, 28 months, 2000; us patent 6,136,472 issued to Barker et al at 24/10/2000; us patent 6,153,333 issued to Barker et al at 9/28/2000; PCT publication WO/01/13443 to Barker et al, published at 22/2/2001; and PCT publication WO/01/54212 to Barker et al, published at 26.7.2001.

In general, the positive electrode material must have a high free energy to react with lithium, be able to insert a large amount of lithium, maintain its lattice structure upon insertion and extraction of lithium, allow rapid diffusion of lithium, provide good electrical conductivity, not be significantly dissolved in the electrolyte system of the battery, and be easily and inexpensively manufactured. However, many cathode materials known in the art lack one or more of these properties. As a result, many of these materials cannot be manufactured at low cost, provide insufficient voltage, have insufficient charge capacity, or lose their ability to be recharged over multiple cycles, for example.

Disclosure of Invention

The present invention provides electrode active materials comprising lithium or other alkali metals, transition metals, phosphates or similar moieties, and halogen or hydroxyl moieties. These electrode active materials have the following general formula:

A_aM_b(XY₄)_cZ_d

in the formula

(a) A is selected from Li, Na, K and their mixture, a is more than 0 and less than or equal to 8;

(b) m is one or more metals, including at least one metal capable of being oxidized to a higher valence state, 1. ltoreq. b.ltoreq.3;

(c)XY₄selected from X' O_4-xY′_x、X′O_4-yY′_2y、X″S₄And mixtures thereof, wherein X' is P, As, Sb, Si, Ge, S and mixtures thereof; x' is P, As, Sb, Si, Ge and mixtures thereof; y' is halogen; x is more than or equal to 0 and less than 3; y is more than 0 and less than 4; c is more than 0 and less than or equal to 3;

(d) z is OH, halogen or a mixture thereof, and d is more than 0 and less than or equal to 6;

wherein M, X, Y, Z, a, b, c, d, X and Y are selected to maintain electroneutrality of the compound.

In a preferred embodiment, M comprises two or more transition metals selected from groups 4 to 11 of the periodic Table of the elements. In another preferred embodiment, M is M 'M ", wherein M' is at least one transition metal selected from groups 4 to 11 of the periodic Table of the elements; m' is at least one element selected from groups 2, 3, 12, 13 or 14 of the periodic Table of the elements. Preferred embodiments are those wherein c is 1, 2 and 3. Preferred embodiments are a ≦ 1 and c ═ 1; a ═ 2 and c ═ 1; a is more than or equal to 3 and c is 3. Preferred embodiments also include materials having a structure similar to the minerals olivine (referred to herein as "olivine") and NASICON (sodium super ion conductor) materials (referred to herein as "NASICON").

The present invention also provides an electrode comprising the electrode active material of the present invention. Also provided is a battery comprising a first electrode having an electrode active material of the invention, a second electrode having a compatible active material, and an electrolyte. In a preferred embodiment, the novel electrode materials of the present invention are used as positive electrode (cathode) active materials, together with compatible negative electrode (anode) active materials, to reversibly cycle lithium ions.

It has been found that the novel electrode materials, electrodes and batteries of the present invention have advantages over such materials and devices of the prior art. These advantages include: increased capacitance, improved cycle performance, increased reversibility, and reduced cost. Specific advantages and embodiments of the invention will become apparent from the detailed description which follows. It should be understood, however, that the detailed description and the specific examples while indicating the preferred embodiment are intended for purposes of illustration only and are not intended to limit the scope of the invention.

Detailed Description

The present invention provides an electrode active material for a battery. The term "battery" as used herein refers to a device comprising one or more electrochemical cells for the production of electricity. Each electrochemical cell comprises a negative electrode, a positive electrode and an electrolyte. Two or more electrochemical cells may be combined, i.e., "stacked," to form a multi-cell having a voltage that is the sum of the voltages of the individual electrochemical cells.

The electrode active material of the present invention may be used for the negative electrode, the positive electrode, or both. Preferably, the active material of the present invention is used for a positive electrode. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor are they intended to be excluded from the scope of the invention

Electrode active material:

the present invention provides active materials (referred to herein as "electrode active materials") comprising lithium or other alkali metals, transition metals, phosphates or similar moieties, and halogen or hydroxyl moieties. These electrode active materials have the general formula A_aM_b(XY₄)_cZ_d. (the word "comprise" and its derivatives, as used herein, are intended to be non-limiting, such that recitation of one does not exclude the other, analogous, materials, compositions, devices, and methods, which may be used in the present invention.)

A is selected from Li (lithium), Na (sodium), K (potassium) and mixtures thereof. In a preferred embodiment, a is Li, or a mixture of Li and Na, a mixture of Li and K, or a mixture of Li, Na and K. In another embodiment, a is Na, or a mixture of Na and K. Preferably, "a" is about 0.1 to about 6, more preferably about 0.2 to about 6. When c is 1, a is preferably from about 0.1 to 3, more preferably from about 0.2 to 2. In a preferred embodiment, when c is 1, a is less than about 1. In another preferred embodiment, when c is 1, a is about 2. When c is 2, a is preferably from about 0.1 to about 6, more preferably from about 1 to about 6. When c is 3, a is preferably from about 0.1 to about 6, more preferably from about 2 to about 6, and still more preferably from about 3 to about 6.

M comprises one or more metals, including at least one metal capable of being oxidized to a higher valence state. In a preferred embodiment, the removal of the alkali metal from the electrode active material is accompanied by a change in the oxidation state of at least one of the metals constituting M. The amount of the metal that can be oxidized in the electrode active material determines the amount of alkali metal that can be removed. These principles are known in the art in common usage, such as in U.S. patent 4,477,541 to spiolii, issued at 16.10.1984, and U.S. patent 6,136,472 to Barker, issued at 24.10.2000, which are all incorporated herein by reference.

See general formula A_aM_b(XY₄)_cZ_dThe amount of alkali metal that can be removed (a ') is equal to the amount of oxidizable metal (b') and the valence (V)^M) Is in the relationship of

a′＝b′(ΔV^M)

In the formula,. DELTA.V^MIs the difference between the readily accessible valence state of the metal in the active material and its actual valence state. (the terms oxidation state and valence state are used interchangeably in the art.) for example, for an active material comprising iron (Fe) in the +2 oxidation state, Δ V^MAs iron can be oxidized to the +3 oxidation state (although in some cases iron can also be oxidized to the +4 oxidation state). If b is 2(2mol iron/1 mol material), the maximum amount (a') of alkali metal (oxidation state +1) that can be removed during cycling of the cell is 2 (i.e. 2mol alkali metal). If the active material contains manganese (Mn) in the +2 oxidation state, Δ V^M2 because manganese can be oxidized to the +4 oxidation state (although Mn can also be oxidized to higher oxidation states in some cases). Thus, in this example, the maximum amount of alkali metal that can be removed during cycling of the cell (a') is 4, assuming a ≧ 4.

M may be one metal or a combination of two or more metals. In embodiments where M is a combination of more than one element, the total valence of M in the active material must be such that the final active material is electrically neutral (i.e., the positive charges of all anionic species in the material are in equilibrium with the negative charges of all cationic species), as will be discussed further below. Purification valency (V) of M with a mixture of more than 1 element (M1, M2 … Mt)^M) Can be represented by the following general formula

V^M＝V^M1b₁+V^M2b₂+…V^Mtb_t

In the formula, b₁+b₂+…b_t＝1，V^M1Is the oxidation state of M1, V^M2Is the oxidation state of M2, and so on. (of M and other Components of the electrode active Material)The net valency will be discussed further below. )

Typically, M may be a metal or metalloid element selected from groups 2-14 of the periodic Table of elements. "group" herein refers to the group number (i.e., column) of the periodic table as defined in the IUPAC periodic table of elements. See, for example, U.S. patent 6,136,472 issued to Barker et al at 24.10.2000, which is incorporated herein by reference. In a preferred embodiment, M is one or more transition metals selected from groups 4-11. In another preferred embodiment, M is a mixture of metal elements M 'M ", wherein M' is at least one transition metal element selected from groups 4 to 11 and M" is at least one element selected from groups 2, 3, 12, 13 or 14.

The transition metals used herein are selected from: ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zr (zirconium), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Cd (cadmium), Hf (hafnium), Ta (tantalum), W (tungsten), Re (rhenium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Hg (mercury), and mixtures thereof. Preferably the transition elements of the first row (period 4 elements of the periodic table) are selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu and mixtures thereof. Particularly preferred transition metals herein include Fe, Co, Mn, Cu, V, Cr and mixtures thereof. In some embodiments, mixtures of transition metals are preferred. Although many oxidation states of these transition metals are useful, in some embodiments, transition metals having a +2 oxidation state are preferred.

M can also be non-transition metals and metalloids. These elements are selected from the group 2 elements, in particular Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium); elements of group 3, in particular Sc (scandium), Y (yttrium), and lanthanides, in particular La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium); elements of group 12, in particular Zn (zinc) and Cd (cadmium); elements of group 13, specifically B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium); elements of group 14, specifically Si (silicon), Ge (germanium), Sn (tin), and Pb (lead); elements of group 15, specifically As (arsenic), Sb (antimony), and Bi (bismuth); an element of group 16, in particular Te (tellurium); and mixtures thereof. Preferred non-transition metals include group 2, 12, 13 and 14 elements. Particularly preferred non-transition metals are selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al and mixtures thereof. Particularly preferred are non-transition metals selected from the group consisting of Mg, Ca, Zn, Ba, Al and mixtures thereof.

As will be discussed further herein, "b" is selected to maintain the electroneutrality of the electrode active material. In a preferred embodiment, when c is 1, b is about 1 to 2, preferably about 1. In another preferred embodiment, when c is 2, b is about 2 to 3, preferably about 2.

XY₄Selected from X' O_4-xY′_x、X′O_4-yY′_2y、X″S₄And mixtures thereof, wherein X' is P (phosphorus), As (arsenic), Sb (antimony), Si (silicon), Ge (germanium), S (sulfur), and mixtures thereof; x' is P, As, Sb, Si, Ge and mixtures thereof. In a preferred embodiment, X 'and X' are each selected from P, Si and mixtures thereof. In a particularly preferred embodiment, X 'and X' are P. Y is halogen, preferably F (fluorine).

In a preferred embodiment, 0 < x < 3, 0 < y < 4, such that XY₄A part of oxygen (O) in the moiety is substituted with halogen. In another preferred embodiment, x and y are 0. In a particularly preferred embodiment, XY₄Is X' O₄In the formula, X' is preferably P or Si, more preferably P.

Z is OH, halogen or a mixture of the above. In a preferred embodiment, Z is selected from OH (hydroxyl), F (fluorine), Cl (chlorine), Br (bromine) and mixtures thereof. In a preferred embodiment, Z is OH. In another preferred embodiment, Z is F, or a mixture of F and OH, Cl or Br. Preferably, "d" is about 0.1 to about 6, more preferably about 0.2 to about 6. When c is 1, d is preferably from about 0.1 to 3, more preferably from about 0.2 to 2. In a preferred embodiment, when c is 1, d is about 1. When c is 2, d is preferably from about 0.1 to about 6, more preferably from about 1 to about 6. When c is 3, d is preferably from about 0.1 to about 6, more preferably from about 2 to about 6, and still more preferably from about 3 to about 6.

The combination of M, X, Y and Z and the values of a, b, c, d, x, and y are selected to maintain the electroneutrality of the electrode active material. "electrically neutral" herein refers to an electrode active material state in which the sum of cationic charge species (e.g., M and X) is equal to the sum of anionic charge species (e.g., Y and Z) in the material. Preferably, XY₄The moiety is composed as a unitary moiety of an anion having a charge of-2, -3, or-4 valency, depending on the choice of X.

In general, the valence state of each constituent element of the electrode active material may be determined with reference to the composition and valence state of other constituent elements of the material. With reference to the general formula A_aM_b(XY₄)_cZ_dThe electroneutrality of the material can be determined using the general formula:

(V^A)a+(V^M)b+(V^X)c＝(V^Y)4c+(V^Z)d

in the formula, V^AIs the purification valence of A, V^MIs the purification valence of M, V^YIs the purification valence of Y, V^ZIs the clean valence of Z. The term "net valence" of a component as used herein refers to (a) the valence state of the element in an active material in a single valence state if the component is a single element; or (b) if a component contains more than one element or is a single element having more than one valence, then the sum of the molar weights of all the valences of all the elements or of all the valences of a single element. The purification valency of each component is represented by the general formula:

(V^A)b＝[(V^A1)a¹+(Val^A2)a²+...(Val^An)aⁿ]/n；a¹+a²+...aⁿ＝a

(V^M)b＝[(V^M1)b¹+(V^M2)b²+...(V^Mn)bⁿ]/n；b¹+b²+...bⁿ＝b

(V^X)c＝[(V^X1)c¹+(V^X2)c²+...(V^Xn)cⁿ]/n；c¹+c²+...cⁿ＝c

(V^Y)c＝[(V^Y1)c¹+(V^Y2)c²+...(V^Yn)cⁿ]/n；c¹+c²+...cⁿ＝c

(V^Z)c＝[(V^Z1)c¹+(V^Z2)c²+...(V^Zn)cⁿ]/n；c¹+c²+...cⁿ＝c

in general, given the valency of X, the value of "c", and the amount of a, the amount and composition of M is selected so long as M comprises at least one metal capable of oxidation. The calculation of the valence of M can be simplified as follows (in the formula, V^A＝1，V^Z＝1)：

For compounds of formula c ═ 1: (V)^M)b＝(V^A)4+d-a-(V^X)

For compounds of formula c ═ 3: (V)^M)b＝(V^A)12+d-a-(V^X)3

a. The values of b, c, d, x and y may form a stoichiometric or non-stoichiometric formula for the electrode active material. In a preferred embodiment, the values of a, b, c, d, x and y are integers, forming the stoichiometric formula. In another preferred embodiment, one or more of a, b, c, d, x and y are non-integer values. However, it should be understood that in the case of compounds having the formula A containing multiple non-stoichiometric amounts_aM_b(XY₄)_cZ_dWhen multiple units are considered, the formula may be stoichiometric. That is, for a general unit formula in which one or more of a, b, c, d, x, or y is a non-integer, the value of each variable becomes an integer value according to the number of units that is the least common multiple of each of a, b, c, d, x, and y. For example, the active material Li₂Fe_0.5Mg_0.5PO₄F is non-stoichiometric. However, when two such units are included in the lattice structure of the material, Li is represented by the formula₄FeMg(PO₄)₂F₂。

One preferred non-stoichiometric electrode active material is of the formula Li_1+zMPO₄F_zThe material represented by the formula, wherein 0 < z.ltoreq.3, preferably 0 < z.ltoreq.1. Another preferred non-stoichiometric electrode active material is of the formula Li_1+zM′_1-yM″_yPO₄F_zThe material represented by the formula, wherein 0 < z < 3, preferably 0 < z < 1, and 0. ltoreq. y < 1. Particularly preferred non-stoichiometric active materials are of the formula Li_1.25Fe_0.9Mg_0.1PO₄F_0.25The materials indicated.

One preferred electrode active material is a compound having the general formula:

Li_aM_b(PO₄)Z_d

in the formula

(a)0.1＜a≤4；

(b) M is M 'M ", wherein M' is at least one transition metal selected from groups 4 to 11 of the periodic Table of the elements; m' is at least one element selected from groups 2, 3, 12, 13 or 14 of the periodic Table of the elements, and 1. ltoreq. b.ltoreq.3;

(c) z is halogen, and d is more than 0.1 and less than or equal to 4;

wherein M, Z, a, b and d are selected to maintain the electroneutrality of the compound.

Preferably, M 'is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof, and more preferably M' is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof. Preferably, M "is selected from Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al and mixtures thereof, and more preferably M" is selected from Mg, Ca, Zn, Ba, Al and mixtures thereof. Preferably, Z is F.

Another preferred embodiment is a compound having the general formula:

Li_aM_b(PO₄)Z_d

in the formula

(a)0.1＜a≤4；

(c) z is OH or a mixture of OH and halogen, d is more than 0.1 and less than or equal to 4;

Preferably, M is M 'M ", wherein M' is at least one transition metal selected from groups 4-11 of the periodic Table of the elements; m' is at least one element selected from groups 2, 3, 12, 13 or 14 of the periodic Table of the elements. Preferably, M 'is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof, and more preferably M' is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof. Preferably, when a is 2 and d is 1, M is not Ni. Preferably, M "is selected from Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al and mixtures thereof, and more preferably M" is selected from Mg, Ca, Zn, Ba, Al and mixtures thereof.

Another preferred embodiment is a compound having the general formula:

A₂M(PO₄)Z_d

in the formula

(a) A is selected from Li, Na, K and their mixture;

(b) m is M'_1-bM”_bWherein M' is at least one transition metal selected from groups 4 to 11 of the periodic Table of the elements; m' is at least one element selected from groups 2, 3, 12, 13 or 14 of the periodic Table of the elements, 0. ltoreq. b < 1;

(c) z is halogen, d is more than 0.1 and less than or equal to 2;

wherein M, Z, b and d are selected to maintain the electroneutrality of the compound.

Preferably, A is Li, or a mixture of Li with Na, K, or a mixture of Na and K. Preferably, M 'is selected from the group consisting of Fe, Co, Mn, Cu, V, Zr, Ti, Cr and mixtures thereof, and more preferably M' is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr and mixtures thereof. Preferably, M "Selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al and mixtures thereof, and more preferably M "is selected from the group consisting of Mg, Ca, Zn, Ba, Al and mixtures thereof. Preferably, Z is F. Preferably, M is not Ni when d ═ 1. In a preferred embodiment, M 'is Fe or Co, M' is Mg, and X is F. A particularly preferred embodiment is Li₂Fe_1-xMg_xPO₄F. Preferred electrode active materials includeLi₂Fe_0.9Mg_0.1PO₄F and Li₂Fe_0.8Mg_0.2PO₄F。

A preferred electrode active material is represented by the general formula Li₂MPO₄F, wherein M is selected from Ti, V, Cr, Mn, Fe, Co, Cu, Zn or their mixture, preferably Fe, Co, Mn or their mixture. Li₂CoPO₄F and Li₂FePO₄F belongs to this preferred combination.

Another preferred embodiment is a compound having the general formula:

A_aM_b(XY₄)₃Z_d

in the formula

(a) A is selected from Li, Na, K and their mixture, 2 ≤ a ≤ 8;

(b) m comprises one or more metals, including at least one metal capable of being oxidized to a higher valence state, 1. ltoreq. b.ltoreq.3;

(c)XY₄selected from X' O_4-xY′_x、X′O_4-yY′_2y、X″S₄And mixtures thereof, wherein X' is P, As, Sb, Si, Ge, S and mixtures thereof; x' is P, As, Sb, Si, Ge and mixtures thereof; y' is halogen; x is more than or equal to 0 and less than 3; y is more than 0 and less than 4;

(d) z is OH, halogen or their mixture, d is more than 0 and less than or equal to 6;

wherein M, X, Y, Z, a, b, d, X and Y are selected to maintain the electroneutrality of the compound.

In a preferred embodimentIn an embodiment, a is Li, or a mixture of Li with Na or K. In another preferred embodiment, a is Na, K or a mixture thereof. In a preferred embodiment, M comprises two or more transition metals selected from groups 4-11 of the periodic Table of the elements, preferably selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr and mixtures thereof. In another preferred embodiment, M is M 'M ", wherein M' is at least one transition metal selected from groups 4 to 11 of the periodic Table of the elements and M" is at least one element selected from groups 2, 3, 12, 13 or 14 of the periodic Table of the elements having a valence of +2. Preferably, M 'is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof, and more preferably M' is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof. Preferably, M "is selected from Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al and mixtures thereof, and more preferably M" is selected from Mg, Ca, Zn, Ba, Al and mixtures thereof. In a preferred embodiment, XY is preferred₄Is PO₄. In another preferred embodiment, X 'is As, Sb, Si, Ge, S and mixtures thereof, X' is As, Sb, Si, Ge and mixtures thereof, and 0 < X < 3. In a preferred embodiment, Z is F, or a mixture of F with Cl, Br, OH, or a mixture thereof. In another preferred embodiment, Z is OH, or OH withMixtures of Cl or Br. Preferred electrode active materials include materials having the general formula:

A_4+dM′M″(PO₄)₃Z_dwherein M 'is a +3 oxidation state transition metal or non-transition metal, and M' is a +2 oxidation state transition metal or non-transition metal;

A_3+dM′M″(PO₄)₃Z_dwherein M 'is a +4 oxidation state transition metal or non-transition metal, and M' is a +2 oxidation state transition metal or non-transition metal;

A₃+dM₂(PO₄)₃Z_dwherein M is a +3 oxidation state transition metal;

A_1+dM₂(PO₄)₃Z_dwherein M is a +4 oxidation state transition metal;

A_5+dM₂(PO₄)₃Z_dwherein M is a +2 oxidation state transition metal, or a mixture thereof with a +2 oxidation state non-transition metal;

A_2+dM₂(SiO₄)₂(PO₄)Z_dwherein M is a +4 oxidation state transition metal;

A_3+2x+dM₂(SiO₄)_3-x(PO₄)_xZ_dwherein M is a +3 oxidation state transition metal;

A_4+dM₂(SiO₄)₃Z_dwherein M is a +4 oxidation state transition metal;

A_6+dM₂(SiO₄)₃Z_dwherein M is a +3 oxidation state transition metal;

A_2+dM₂(SO₄)₃Z_dwherein M is a +2 oxidation state transition metal, or a mixture thereof with a +2 oxidation state non-transition metal;

A_1+dM′M″(SO₄)₃Z_dwherein M 'is a +2 oxidation state metal, M' is a +3 oxidation state transition metal;

in a preferred embodiment of the present invention, the following electrode active materials and their mixtures are preferred:

Li₂Fe_0.8Mg_0.2PO₄F；Li₂Fe_0.5Co_0.5PO₄F；Li₃CoPO₄F₂；KFe(PO3F)F；

Li₂Co(PO₃F)Br₂；Li₂Fe(PO₃F₂)F；Li₂FePO₄Cl；Li₂MnPO₄OH；Li₂CoPO₄F；Li₂Fe_0.5Co_0.5PO₄F；

Li₂Fe_0.9Mg_0.1PO₄F；Li₂Fe_0.8Mg_0.2PO₄F；Li_1.25Fe_0.9Mg_0.1PO₄F_0.25；Li₂MnPO₄F；Li₂CuPO₄F；

K₂Fe_0.9Mg_0.1P_0.5As_0.5O₄F；Li₂MnSbO₄OH；Li₂Fe_0.6Co_0.4SbO₄Br；Na₃CoAsO₄F₂；

LiFe(AsO₃F)Cl；Li₂Co(As_0.5Sb_0.5O₃F)F₂；K₂Fe(AsO₃F₂)F；Li₂NiSbO₄F；Li₂FeAsO₄OH；

Li₃Mn₂(PO₄)₃F；Na₄FeMn(PO₄)₃OH；Li₄FeV(PO₄)₃Br；Li₃VAl(PO₄)₃F；K₃MgV(PO₄)₃Cl；

LiKNaTiFe(PO₄)₃F；Li₄Fe₂(PO_3.82F_0.68)₃；Li₃FeMn(PO_3.67F_0.33)₃；Li₄Ti₂(PO₄)₃Br；

Li₃V₂(PO₄)₃F₂；Li₆FeMg(PO₄)₃OH；Li₃Mn₂(AsO₄)₃F；K₄FeMn(AsO₄)₃OH；

Li₄FeV(P_0.5Sb_0.5O₄)₃Br；LiNaKAlV(AsO₄)₃F；K₃MgV(SbO₄)₃Cl；Li₃TiFe(SbO₄)₃F；

Li₄Fe₂(SbO_3.82F_0.68)₃；Li₃FeMn(P_0.5As_0.5O_3.67F_0.33)3；Li₄Ti₂(PO₄)₃F；Li_3.25V₂(PO₄)₃F_0.25；

Li₃Na_0.75Fe₂(PO₄)₃F_0.75；Na_4.5Fe₂(PO₄)₃(OH)Cl_0.5；K₈Ti₂(PO₄)₃F₃Br₂；K₈Ti₂(PO₄)₃F₅；

Li₂Ti₂(PO₄)₃F；LiNa_1.25V₂(PO₄)₃F_0.5Cl_0.75；K_1.25Mn₂(PO₄)₃OH_0.25；

LiNa_1.25KTiV(PO₄)₃(OH)_1.25Cl；Na₆Ti₂(PO₄)₃F₃Cl₂；Li₇Fe₂(PO₄)₃F₂；Li₈FeMg(PO₄)₃F_2.25Cl_0.75；

Li₅Na_2.5TiMn(PO₄)₃(OH)₂Cl_0.5；Na₃K_4.5MnCa(PO₄)₃(OH)_1.5Br；K₉FeBa(PO₄)₃F₂Cl₂

Li₅Ti₂(SiO₄)₂(PO₄)F₂；Na₆Mn₂(SiO₄)₂(PO₄)F₂Cl；Li₅TiFe(PO₄)₃F；Na₄K₂VMg(PO₄)₃FCl；

Li₄NaAlNi(PO₄)₃(OH)；Li₃K₃FeMg(PO₄)₃F₂；Li₂Na₂K₂CrMn(PO₄)₃(OH)Br；Li₄TiCa(PO₄)₃F；

Li₄Ti_0.75Fe_1.5(PO₄)₃F；Li₃NaSnFe(PO₄)₃(OH)；Li₃NaGe_0.5Ni₂(PO₄)₃(OH)；

Na₃K₂VCo(PO₄)₃(OH)Cl；Li₃Na₂MnCa(PO₄)₃F(OH)；Li₃NaKTiFe(PO₄)₃F；

Li₆FeCo(SiO₄)₂(PO₄)F；Li₃Na₃TiV(SiO₄)₂(PO₄)F；K_5.5CrMn(SiO₄)₂(PO₄)Cl_0.5；

Li₃Na_2.5V₂(SiO₄)₂(PO₄)(OH)_0.5；Na_5.25FeMn(SiO₄)₂(PO₄)Br_0.25；Li₄NaVTi(SiO₄)₃F_0.5Cl_0.5；

Na₂K_2.5ZrV(SiO₄)₃F_0.5；Li₄K₂MnV(SiO₄)₃(OH)₂；Li₂Na₂KTi₂(SiO₄)₃F；K₆V₂(SiO₄)₃(OH)Br；

Li₈FeMn(SiO₄)₃F₂；Na₃K_4.5CoNi(SiO₄)₃(OH)_1.5；Li₃Na₂K₂TiV(SiO₄)₃(OH)_0.5Cl_0.5；

K₉VCr(SiO₄)₃F₂Cl；Li₄Na₄V₂(SiO₄)₃FBr；Li₄FeMg(SO₄)F₂；Na₂KNiCo(SO₄)(OH)；

Na₅MnCa(SO₄)F₂Cl；Li₃NaCuBa(SO₄)FBr；Li_2.5K_0.5FeZn(SO₄)F；Li₃MgFe(SO₄)₃F₂；

Li₂NaCaV(SO₄)₃FCl；Na₄NiMn(SO₄)₃(OH)₂；NaKBaFe(SO₄)₃F；Li₂KCuV(SO₄)₃(OH)Br；

Li_1.5CoPO₄F_0.5；Li_1.25CuPO₄F_0.25；Li_1.75FePO₄F_0.75；Li_1.66MnPO₄F_0.66；Li_1.5Co_0.75Ca_0.25PO₄F_0.5；

Li_1.75Co_0.8Mn_0.2PO₄F_0.75；Li_1.25Fe_0.75Mg_0.25PO₄F_0.25；Li_1.66Cu_0.6Zn_0.4PO₄F_0.66；

Li_1.75Mn_0.8Mg_0.2PO₄F_0.75；Li₂CuSiF₆；LiCoSiO₄F；Li₂CoSiO₄F；KMnSiO₄Cl；KMn₂SiO₄Cl；

Li₂VSiO₄(OH)₂；LiFeCuSiO₄F₂；LiFeSiO₃F₃；NaMnSiO₃F₄；Li₂CuSiO₃Cl₃；Li₂CuGeF；

Li₂FeGeF；LiCoGeO₄F；Li₂CoGeO₄F；Li₃CoGeO₄F；NaMnSi_0.5Ge_0.5O₄Cl；Li₂TiGeO₄(OH)₂；

LiFeCuGeO₄F₂；NaFeSi_0.5Ge_0.5O₃F₃；LiNaCuGeO₃Cl₃；Li₅Mn₂(SiO₄)₃FCl；

Li₂K₂Mn₂(SiO₄)₃F；Na₃Mn(SiO_3.66F_0.39)OH；Li₄CuFe(GeO₄)₃Cl；Li₃Mn₂(GeO₄)₃OH；

Na₃K₂Mn₂(Si_0.5Ge_0.5O₄)₃F₂；Li₄Mn₂(GeO₄)₃F；KLi₂Fe₂(Si_0.5Ge_0.5O₄)Br，Li₄Fe(GeO_3.66F_0.39)₃F；

Na₃Mn(GeO_3.66F_0.39)OH；LiMnSO₄F；NaFe_0.9Mg_0.1SO₄Cl；LiFeSO₄F；LiMnSO₄OH；

KMnSO₄F；Li₄Mn₃(SO₄)₃OH；Li₅Fe₂Al(SO₄)₃Cl；Li₄Fe(SO_1.32F_2.63)₃BrCl；

Na₃Mn(SO_1.32F_2.68)₃OH；Li₂FeAl(SO_1.32F_2.68)₃F；

Li₂FeZn(PO₄)F₂；Li_0.5Co_0.75Mg_0.5(PO₄)F_0.75；Li₃Mn_0.5Al_0.5(PO₄)F_3.5；Li_0.75VCa(PO₄)F_1.75；

Li₄CuBa(PO₄)F₄；Li_0.5Mn_0.5Ca(PO₄)(OH)_1.5；Li_1.5FeMg(PO₄)(OH)Cl；LiFeCoCa(PO₄)(OH)₃F；

Li₃CuBa(PO₄)(OH)₂Br₂；Li_0.75Mn_1.5Al(PO₄)(OH)_3.75；Li₂Co_0.75Mg_0.25(PO₄)F；

LiNaCo_0.8Mg_0.2(PO₄)F；NaKCu_0.5Mg_0.5(PO₄)F；LiNa_0.5K_0.5Fe_0.75Mg_0.25(PO₄)F；

Li_1.5K_0.5V_0.5Zn_0.5(PO₄)F₂；Li₆CuCa(SbO₂F₄)₃F；Na₆Fe₂Mg(PS₄)₃(OH₂)Cl；

Li₄K₃CoAl(AsO₂F₄)₃F₃；Li₄Fe_1.5Co_0.5(PO₃F)₃(OH)_3.5；K₈FeMg(PO₃F)₃F₃Cl₃Li₅Fe₂Al(SO₄)₃Cl；

LiFe₂(SO₄)₃Cl，LiMn₂(SO₄)₃F，Li₃Ni₂(SO₄)₃Cl，Li₃Co₂(SO₄)₃F，Li₃Fe₂(SO₄)₃Br，

Li₃Mn₂(SO₄)₃F，Li₃MnFe(SO₄)₃F，Li₃NiCo(SO₄)₃Cl；LiMnSO₄F；LiFeSO₄Cl；LiNiSO₄F；

LiCoSO₄Cl；LiMn_1-xFe_xSO₄F，LiFe_1-xMg_xSO₄F；Li₇ZrMn(SiO₄)₃F，Li₇MnCo(SiO₄)₃F，

Li₇MnNi(SiO₄)₃F，Li₇VAl(SiO₄)₃F；Li₄MnCo(PO₄)₂(SiO₄)F；Li₄VAl(PO₄)₂(SiO₄)F；

Li₄MnV(PO₄)₂(SiO₄)F；Li₄CoFe(PO₄)₂(SiO₄)F；Li_0.6VPO₄F_0.6；Li_0.8VPO₄F_0.8；LiVPO₄F；

Li₃V₂(PO₄)₂F₃；LiVPO₄Cl；LiVPO₄OH；NaVPO₄F；Na₃V₂(PO₄)F；

the manufacturing method comprises the following steps:

has a general formula A_aM_b(XY₄)_cZ_dIs readily synthesized by reaction of the starting materials in a solid state reaction with or without oxidation or reduction of the metal species contained. Depending on the desired values of a, b, c and d in the product, it is possible to choose a product containing "a" moles of all sources of alkali metal A, "b" moles of all sources of metal M,"c" moles of all sources of phosphate (or other XY)₄Species), and "d" moles of all sources of halide or hydroxide Z starting material. As described below, a specific starting material may be A, M, XY₄Or a source of more than one component of Z. Alternatively, the reaction may be carried out with an excess of one or more starting materials. In this case, the stoichiometry of the product may be determined by component A, M, XY₄And the limiting component in Z. Since in this case at least some of the starting materials will remain in the mixture of reaction products, it is generally necessary to provide the exact molar amount of all starting materials.

Sources of alkali metals include any of a number of salts or ionic compounds of lithium, sodium, potassium, rubidium or cesium. Lithium, sodium and potassium compounds are preferred. Preferably, the alkali metal source is provided in powder or granular form. Many such materials are known in the field of inorganic chemistry. Non-limiting examples include: lithium, sodium and/or potassium fluoride, chloride, bromide, iodide, nitrate, nitrite, bisulfate, sulfite, bisulfite, carbonate, bicarbonate, borate, phosphate, hydrogenphosphate, dihydrogenphosphate, silicate, antimonate, arsenate, germanite (germines), oxide, acetate, oxalate, and the like. Hydrates of the above compounds, as well as mixtures, may also be used. In particular, the mixture may contain more than one alkali metal, thereby producing a mixed alkali metal active material in the reaction.

Sources of the metal M include salts or compounds of transition metals, alkaline earth metals or lanthanides, and non-transition metals, such as any of aluminum, gallium, indium, thallium, tin, lead and bismuth. Non-limiting metal compounds include: fluoride, chloride, bromide, iodide, nitrate, nitrite, sulfate, bisulfate, sulfite, bisulfite, carbonate, bicarbonate, borate, phosphate, hydrogenphosphate, dihydrogenphosphate, silicate, antimonate, arsenate, germanite, oxide, hydroxide, acetate, oxalate, and the like. Hydrates may also be used, as well as mixtures of metals, mixtures of metals with alkali metals, to produce alkali metal mixed metal active materials. The metal M in the starting material may be in any oxidation state, determined according to the desired oxidation state in the desired product and the oxidation or reduction conditions to be employed, as described below. The metal source is selected so that at least one metal in the final reaction product is capable of having a higher oxidation state than its oxidation state in the reaction product.

In addition to phosphates (or other XY)₄Species), halides or hydroxide sources, the desired source of starting material anions, such as phosphates, halides and hydroxides, are provided by some salts or compounds containing cations having a positive charge. These cations include, but are not limited to: metal ions, such as alkali metals, transition metals or other non-transition metals, and complex cations, such as ammonium or quaternary ammonium. The phosphate anion in these compounds may be phosphate, hydrogen phosphate or dihydrogen phosphate. As the above-mentioned alkali metal source and metal source, it is preferable to provideThe starting material of the phosphate, halide or hydroxide is in the form of granules or powder. Hydrates of the above compounds may also be usedAnd mixtures thereof.

As is evident from the above, the starting material may provide A, M, XY₄And Z. In various embodiments of the present invention, a starting material is provided that combines, for example, an alkali metal and a halide, or a metal and a phosphate. Thus, fluorides such as lithium, sodium or potassium may be reacted with metal phosphates such as vanadium or chromium phosphates, or with mixtures of metal compounds such as metal phosphates and metal hydroxides. In one embodiment, a starting material is provided that contains an alkali metal, a metal, and a phosphate. According to the simple degree of acquisition, the method can sufficiently flexibly select the alkali metal A, the metal M and the phosphate (or other XY)₄Part), and a halide/hydroxide Z. Mixtures of starting materials providing the various components may also be used.

In general, any anion can be combined with the alkali metal cation to provide the starting material for the alkali metal source, or combined with the metal M cation to provide the starting material for metal M. Likewise, any cation may be combined with a halide or hydroxide anion to provide the starting material for the Z component source, and any cation may be used as a phosphate or similar XY₄Part of the counterions. However, it is preferred to select starting materials with counterions that produce volatile byproducts. The starting materials with these counterions form volatile by-products such as water, ammonia and carbon dioxide, which can be easily removed from the reaction product. This principle will be described in detail in some embodiments below.

Heating component A, M, phosphate (or other XY) for a time and at a temperature sufficient to produce a reaction product₄Part) and the starting materials of the Z source may be reacted together in the solid state. The starting material is provided in the form of a powder or granules. The powders are mixed together by any of a variety of procedures, such as ball milling without attrition, mixing with a bowl and pestle, and the like. Subsequently, the mixture of powdered starting materials is pressed into small pieces and/or held together with a binder material to form a densely combined reaction mixture. Placing the reaction mixture in a furnaceHeating is carried out until reaction products are formed, the heating temperature being generally above about 400 ℃. However, when Z in the active material is a hydroxide, it is desirable to heat at a lower temperature to avoid volatilization of water rather than entrance of hydroxyl groups into the reaction product. The temperature and time of the reaction are given in some of the examples below.

When the starting material contains hydroxyl groups for incorporation into the reaction product, the reaction temperature is preferably less than about 400 deg.C, more preferably less than about 250 deg.C. One way to achieve the above temperatures is to carry out the reaction in hot water, as described in examples 15-16. In the hydrothermal reaction, a small amount of liquid, such as water, is mixed with the starting materials and placed in a pressurized vessel. The reaction temperature is limited to the temperature that can be reached by heating the liquid under pressure.

The reaction may be carried out under conditions that do not produce redox, or under reducing or oxidizing conditions, if desired. When the reaction is carried out under conditions that do not produce redox, the oxidation state of the metal or mixed metals in the reaction product is the same as in the starting material. This embodiment is shown in example 16. As for the oxidation conditions, it can be provided by carrying out the reaction in air. For example, using oxygen from air in example 12, cobalt in the starting material having an average oxidation state of +2.67(8/3) was oxidized to the +3 oxidation state in the final product.

Reduction may also occur during the reaction. For example, the reaction may be carried out in a reducing atmosphere, such as an atmosphere of hydrogen, ammonia, methane, or a reducing gas mixture. Alternatively, the reduction may be carried out in situ by adding a reducing agent to the reaction mixture which will participate in the reaction to reduce the metal M, but the by-products produced should not have an effect on the later active material when used in an electrode or battery. One conventional reducing agent used to make the active materials of the present invention is carbon used as the reduction. In a preferred embodiment, the reaction is carried out in an inert atmosphere, such as argon, nitrogen or carbon dioxide. Such reducing carbon is conveniently provided by elemental carbon, or by an organic material capable of decomposing under the reaction conditions, to form elemental carbon or a similar reducing carbon-containing substance. The organic materials include, without limitation, glycerol, starch, sugars, coke, and organic polymers that carbonize or pyrolyze under reaction conditions to form reducing carbon. The preferred source of reducing carbon is elemental carbon. Carbothermic reduction is shown in examples 7, 19 and 21.

Can be prepared according to the initial composition A, M, PO₄(or other XY)₄Moiety) and the relative stoichiometry of Z select the stoichiometry of the reduction. If desired, it is generally not difficult to add the reducing agent in excess of the stoichiometric amount and to remove the excess reducing agent after the reaction. In the case of using a reducing gas and a reducing carbon, such as elemental carbon, an excess amount of the reducing agent does not cause a problem. In the former case, the gas will volatilize, i.e., be easily separated from the reaction mixture, while in the latter case, the remaining carbon in the reaction product will not affect the properties of the active material, since carbon is typically added to the active material to form the electrode material for the electrochemical cells and batteries of the present invention. The by-products carbon monoxide or carbon dioxide (in the case of carbon) or water (in the case of hydrogen) are readily removed from the reaction mixture.

The reaction stoichiometry of the mixture of starting material and hydrogen is shown in the following table, which gives the product formed when the starting material is reacted with "n" moles of hydrogen according to the following reaction:

nH₂+Li₂CO₃+M₂O₅+LiF+3NH₄H₂PO₄→ reaction product (shown in the table below)

Value of "n	Reaction product	Volatilized by-product
Value of "n	Reaction product	Volatilized by-product	1	Li₂M₂(PO₄)₃F	0.5CO₂+3NH₃+5.5H₂O
1.5	Li₃M₂(PO₄)₃F	CO₂+3NH₃+6H₂O	1	Li₂M₂(PO₄)₃F	0.5CO₂+3NH₃+5.5H₂O
1.5	Li₃M₂(PO₄)₃F	CO₂+3NH₃+6H₂O	2.5	Li₃M₂P₃O₁₁F	CO₂+3NH₃+7H₂O

The progress of the reaction is not solely dependent on the amount of hydrogen (always used in excess). It also depends on the temperature of the reaction. Higher temperatures will help to generate greater reducing power.

In addition, in the reaction product, for example, (PO) is obtained₄)₃F or P₃O₁₁F, determined by the thermodynamics of the product formation. Lower energy products are readily produced.

M in the starting material at a temperature at which only 1 mole of hydrogen is reacted⁵⁺Reduction to M⁴⁺To accommodate 2 lithium in the reaction product. When 1.5 moles of hydrogen are reacted, M is added in view of the stoichiometry of the reduction⁵⁺Average reduction to M^+3.5. When 2.5 moles of hydrogen are used, M⁵⁺Average reduction to M^+2.5. At this point, there is not enough lithium to equilibrate with other metals in the equilibration reaction (PO)₄)₃Charge of-10 valence of the F group. Thus, the reaction product is P having a charge of-8₃O₁₁The F group, to balance the charge. In the above table is shown when A of the present invention is synthesized_aM_b(PO₄)_cZ_dThe importance of all stoichiometric relationships is taken into account when active materials.

When a reducing atmosphere such as hydrogen is used, it is difficult to supply the reducing gas without excess. In this case, it is preferred to provide additional limiting reactants to control the stoichiometry of the reaction, as shown in the above table. Alternatively, the reduction may be carried out in the presence of a reducing carbon, such as elemental carbon. Experimentally, the precise amount of reductant carbon shown in the table can be used in place of the reductant hydrogen to produce a selected stoichiometric product. However, it is preferred to conduct the carbothermic reduction with a 1 molar excess of carbon. This is also experimentally facilitated, as with a reducing atmosphere, and the resulting product contains an excess of carbon dispersed therein, which, as noted above, provides a useful active electrode material.

Carbothermic reduction methods for synthesizing mixed metal phosphates are described in PCT publication WO/01/53198 by Barker et al, incorporated herein by reference. Carbothermic reduction processes may be used to react the starting materials in the presence of reducing carbon to form various products. The carbon acts to reduce the metal ions in the source of starting material metal M. Reducing carbon, for example in the form of elemental carbon powder, is mixed with other starting materials and heated. For best results, the temperature should be above about 400 ℃ and up to about 950 ℃. Higher temperatures may also be used, but are generally not required.

Typically, high temperature (about 650-₂. High temperature reactions produce CO emissions, the stoichiometry of which requires the use of CO produced at low temperatures₂More carbon than is the case for emissions. This is because C generates CO₂Is stronger than the reduction of C to CO. C to CO₂The reaction of (a) increases the oxidation state of carbon to +4 (from 0 to 4), and the reaction of (C) to CO increases the oxidation state of carbon to +2 (from ground state 0 to 2). In principle, this influences the reaction schedule, since not only the stoichiometry of the reducing agent, but also the reaction schedule is taken into accountThe temperature of the reaction. However, when an excessive amount of carbon is used, there is no such concern. Therefore, it is preferable to use an excess of carbon and to control the stoichiometry of the reaction with another starting material as a limiting reactant.

As described above, the active material A of the present invention_aM_b(XY₄)_cZ_dMay contain mixtures of alkali metals A, mixtures of metals B, mixtures of component Z and mixtures of compounds of the general formula₄A phosphate group as shown. In another aspect of the invention, the phosphate groups may be wholly or partially substituted with some other XY₄Partial substitution, also known as "phosphate substitutes" or "modified phosphates". Thus, the present invention provides active materials in which XY is₄The part being wholly or partly covered by some part, e.g. Sulphate (SO)₄ ^2-) Monofluoro-monophosphoric acid radical (PO)₃F^2-) Difluoro monophosphate (PO)₂F^2-) Silicic acid radical (SiO)₄ ^4-) Arsenate and antimonateAnd phosphate groups substituted with germanate. Analogs of the above-described oxy-radical groups (in which some or all of the oxygen is replaced by sulfur) can also be used in the active materials of the present invention, except that the sulfate group may not be fully replaced by sulfur. For example, thiophosphoric acid salts may also be used as materials that replace all or part of the phosphate in the active materials of the present invention. The thiophosphoric acid radical comprises an anionic PO₃S^3-、PO₂S₂ ^3-、POS₃ ^3-And PS₄ ^3-. They can be conveniently used as sodium, lithium or potassium derivatives.

To synthesize active materials containing modified phosphate moieties, all or part of the phosphate compound can be substituted, typically with a source of a replacement anion as described above. Such substitution is believed to be on a stoichiometric basis and the starting material providing the source of the replacement anions is provided along with the other starting materials described above. The synthesis of the active material containing modified phosphate groups is carried out as described above, either without redox or under oxidizing or reducing conditions. As with the phosphate compounds, compounds containing modified or substituted phosphate groups may also be sources of other components of the active material. For example, the alkali metal and/or mixed metal M may be part of a modified phosphate compound.

Non-limiting examples of sources of monofluorophosphate include Na₂PO₃F、K₂PO₃F、(NH₄)₂PO₃F·H₂O、LiNaPO₃F·H₂O、LiKPO₃F、LiNH₄PO₃F、NaNH₄PO₃F、NaK₃(PO₃F)₂And CaPO₃F·2H₂And O. Representative examples of sources of difluoromonophosphate compounds include, without limitation, NH₄PO₂F₂、NaPO₂F₂、KPO₂F₂、Al(PO₂F₂)₃And Fe (PO)₂F₂)₃。

When necessary, by partial or total substitution of siliconAs phosphorus in the material, a wide variety of silicates and other silicon-containing compounds can be used. For example, silicon sources useful in the active materials of the present invention include: orthosilicate, disilicate, or cyclosilicate anions, e.g. Si₃O₉ ^6-、Si₆O₁₈ ^12-Etc., and are represented by the general formula (SiO)₃ ^2-)_nFor example, LiAl (SiO)₃)₂Indicating pyrocene. Silicon dioxide may also be used. Example 23 shows partial substitution of phosphate with silicate.

Representative arsenate compounds which may be used to prepare the active materials of the present invention include H₃AsO₄And anions [ H ]₂AsO₄]^-And [ HAsO ]₄]^2-A salt. The antimonate source in the active material may be formed from an antimony-containing material, such as Sb₂O₅、M¹SbO₃(in the formula, M¹Is a metal in oxidation state +1), M^IIISbO₄(in the formula, M^IIIIs a metal in oxidation state + 3), and M^IISb₂O₇(in the formula, M^IIIs a metal in oxidation state + 2). Other antimonate sources include compounds such as Li₃SbO₄、NH₄H₂SbO₄And [ SbO ]₄]^3-Mixed salts of other alkali metals and/or ammonium of the anion. Example 24 shows partial substitution of phosphate with antimonate.

The source of the sulfate compound of phosphorus in the active material may be partially or fully replaced with sulfur, including alkali and transition metal sulfates and bisulfates, as well as mixed metal sulfates, such as (NH)₄)₂Fe(SO₄)₂、NH₄Fe(SO₄)₂And the like. Finally, when it is desired to replace some or all of the phosphorus in the active material with germanium, germanium-containing compounds such as GeO may be used₂。

To prepare active materials containing modified phosphate groups, it is necessary to select the stoichiometry of the starting materials in accordance with the stoichiometry required for the modified phosphate groups in the final product, and to react the starting materials together in accordance with the procedures described above in connection with the phosphate materials. Naturally, the partial or complete substitution of the phosphate groups with any of the above-described modified or substituted phosphate groups necessarily requires a recalculation of the required stoichiometry of the starting materials.

In a preferred embodiment, the preparation is carried out in a two-stage process from Li of the formula_1+xMPO₄F_xA compound of the formula which comprises first preparing LiMPO₄Compound (step 1), then reacted with x moles of LiF to give Li₂MPO₄And F (step 2). The starting (precursor) materials used in step 1 include lithium-containing compounds, metal-containing compounds, and phosphate-containing compounds. Each of these compounds may be used alone or added to the same compound, such as a lithium metal compound or a metal phosphate compound.

Following the preparation described in step 1, a reaction step 2 is performed to react the lithium metal phosphate (provided in step 1) with a lithium salt, preferably lithium fluoride (LiF). LiF is mixed with lithium metal phosphate in a ratio to provide a lithiated transition metal fluorophosphate product. Lithiated transition metal fluorophosphates have the ability to provide lithium ions to the electrochemical potential.

In addition to the two-step process described above, a one-step reaction process can also be used to prepare these preferred materials of the present invention. In one method of the invention, the starting materials are first mixed thoroughly and then reacted together under heat. Typically, the mixed powders are compressed into small pieces. The tablets are then heated to a suitably high temperature. The reaction may be carried out in an air atmosphere or a non-oxidizing atmosphere. In another approach, the lithium metal phosphate compound used as a precursor in the lithiated transition metal fluorophosphate reaction can be formed by a carbothermal reduction reaction or a hydrogen reduction reaction.

The synthetic routes described above are generally applicable to a variety of starting materials. The metal compound may be reduced in the presence of a reducing agent such as hydrogen or carbon. The same applies to other metals and phosphate-containing starting materials. Thermodynamic considerations, such as the ease of reduction of the starting materials selected, the reaction kinetics, and the melting point of the salt, all result in adjustments to conventional procedures, such as adjustments to the amount of reducing agent, reaction temperature, and residence time.

The first step of the preferred two-step process involves reacting a lithium-containing compound (lithium carbonate Li)₂CO₃) Metal-containing compound having phosphate group (e.g., nickel phosphate Ni)₃(PO₄)₂·xH₂O, typically with more than 1 mole of water) with a phosphoric acid derivative (e.g., diammonium phosphate DAHP). These powders were premixed with a mortar and pestle until they were uniformly dispersed, but various other methods may be used. The mixed powder of starting materials is pressed into small pieces. The first stage reaction is carried out by heating the chips in a furnace to a suitably high temperature and holding at that temperature for several hours at a preferred heating rate. The tablets were heated to the preferred temperature of about 800 c using the preferred ramp rate (about 2 c/min). While the rate of heating is important to the reaction in many cases, it is not always a critical factor in the success or failure of the reaction. The reaction is carried out under a flowing air atmosphere (e.g., when M is Ni or Co), but the reaction may also be carried out under an inert atmosphere, such as N₂Or Ar (when M is Fe). The flow rate is determined according to the size of the furnace and the amount required to maintain the atmosphere. The reaction mixture is maintained at an elevated temperature for a period of time sufficient to form the reaction product. The chips were then cooled to ambient temperature. The cooling rate of the sample may also be varied.

In step 2, Li₂MPO₄F active Material by LiMPO prepared in step 1₄The precursor is prepared by reaction with a lithium salt, preferably lithium fluoride LiF. Alternatively, the precursor may include a lithium salt other than a halide (e.g., lithium carbonate) and a halide material other than lithium fluoride (e.g., ammonium fluoride). The precursors used in step 2 were first premixed with a bowl and pestle until they were uniformly dispersed. They are then formed into small pieces, for example, using a manual tablet press and a die having a diameter of about 1.5 ". The resulting chips are preferably about 5mm thick and uniform. The chips were then fed into a temperature controlled box furnace and heatedPreferably at a ramp rate of about 2 c/minute to a final temperature of about 800 c. The entire reaction was carried out in a flowing argon atmosphere. The pieces were cooled to room temperature before being removed from the box furnace. As mentioned above, the speed of cooling the chips appears to have no direct effect on the product.

Examples 1-6 and 8 illustrate the two-step reaction process described above, while examples 7 and 11-13 illustrate the one-step process. Example 9 presents a two-step procedure for making the sodium-containing active material of the present invention.

Another embodiment of the present invention is the preparation of mixed lithium metal fluorophosphate compounds. Example 6 shows the general formula Li obtained in a two-step reaction₂M′_xM″_1-xPO₄In general, in the first step, lithium or other alkali metal compound, at least two metal compounds, and a phosphate are salifiedThe compounds are reacted together to provide a lithium mixed metal phosphate precursor. The powders were mixed together and made into small pieces as described in the other reactions. The chips are then fed into a temperature-controlled box furnace into which a flowing inert gas (e.g., argon) is introduced. The sample is then heated to a final temperature of about 750 c at a ramp rate of, for example, about 2 c/min and maintained at that temperature for 8 hours or until reaction products are formed. As can be seen from the various examples, the particular temperature used is determined by the initial compounds used to form the precursor, but the criteria described are not intended to limit the invention to these compounds in any way. In particular, since a carbothermic reduction reaction occurs during the formation of the precursor, it is necessary to use a high temperature. After the chips were heated for a prescribed time, they were cooled to room temperature.

The second step is the reaction of a lithium mixed metal phosphate compound and an alkali metal halide, such as lithium fluoride. After producing chips from the lithium mixed metal phosphate precursor and lithium fluoride, the chips were placed in a covered and sealed nickel crucible and fed into a box furnace. Typically, a nickel crucible is a convenient container for the chips, but other suitable containers, such as ceramic crucibles, may be used. The sample was then rapidly heated to a final temperature of about 700 c and held at that temperature for about 15 minutes. The crucible was then removed from the box furnace and cooled to room temperature. The lithiated transition metal fluorophosphate compounds of the present invention are obtained.

Except that Li is provided by the general formula₂M′_xM″_1-xPO₄Example 8 provides, in addition to the compound represented by F, a compound represented by the general formula Li_1+zM′_yM″_1-yPO₄F_zShown is a non-stoichiometric fluorophosphate salt mixed with metallic lithium. In the preparation of a non-stoichiometric amount of a compound of formula (la), the same conditions as for the preparation of a stoichiometric amount of a compound of formula (lb) are satisfied, as described in example 6. In example 8, the molar ratio of lithiated transition metal phosphate precursor to lithium fluoride is about 1.0 to about 0.25. The precursor compounds were premixed using a bowl and pestle and made into small pieces. The pieces were then placed in a covered and sealed crucible and transferred to a box furnace. The sample was rapidly heated to a final temperature of about 700 c and held at that temperature for about 15 minutes. In the preparation of a polymer of the formula Li_1+zMPO₄F_zSimilar conditions were used for the compounds indicated.

Referring back to the description of the reaction of lithium fluoride and metal phosphate, the preferred reaction temperature is about 400 ℃ or greater, but below the melting point of the metal phosphate, more preferably about 700 ℃. Preferably less than one degree to about 10 deg.c/minute, more preferably about 2 deg.c/minute. After the desired temperature is reached, the reaction is maintained at the reaction temperature for about 10 minutes to several hours, depending on the reaction temperature selected. The heating may also be carried out under an air atmosphere, or, if desired, under a non-oxidizing or inert atmosphere. After the reaction, the product is cooled from the elevated temperature to ambient temperature (room temperature, i.e., about 10-40 ℃). Ideally, the cooling rate is about 50 deg.C/min. It has been found that in some cases, this cooling can result in the desired structure of the final product. The product may also be quenched at a cooling rate of about 100 deg.c/min. In some cases, such rapid cooling is preferred. It has been found that the above cooling rate ranges are not suitable for certain situations and, therefore, the cooling rate requirements need to be changed. An electrode:

the present invention also provides an electrode comprising the electrode active material of the present invention. In a preferred embodiment, the electrode of the present invention comprises the electrode active material of the present invention, a binder, and a conductive carbonaceous material.

In a preferred embodiment, the electrode of the present invention comprises:

(a) about 25% to about 95%, more preferably about 50% to about 90%, of the active material;

(b) about 2-95% of a conductive material (e.g., carbon black);

(c) about 3-20% of a binder for keeping all particulate materials in contact with each other, but without reducing the ionic conductivity.

(unless otherwise indicated, all parts herein are parts by weight). Preferably, the positive electrode of the present invention comprises about 50-90% of the active material, about 5-30% of the conductive material, and the balance of the binder. Preferably, the negative electrode of the present invention comprises about 50-95 wt% of a conductive material (e.g., preferably graphite), with the balance being a binder.

Conductive materials for use herein include carbon black, graphite, powdered nickel, metal particles, conductive polymers (e.g., materials characterized by conjugated networks of double bonds, such as polypyrrole and polyacetylene), and mixtures thereof. Preferably, the adhesive used herein comprises a polymeric material and an extractable plasticizer suitable for forming a bonded porous composite. Preferred adhesives include: halogenated hydrocarbon polymers such as vinylidene chloride and polydichloro-1, 4-phenylene ethylene, fluorinated polyurethanes, fluorinated epoxies, fluorinated acrylics, copolymers of halogenated hydrocarbon polymers, epoxies, Ethylene Propylene Diene Monomer (EPDM), polyvinylidene fluoride (PVDF), Hexafluoropropylene (HFP), Ethylene Acrylic Acid (EAA), Ethylene Vinyl Acetate (EVA), EAA/EVA copolymers, PVDF/HFP copolymers, and mixtures thereof.

In a preferred method of making an electrode, the electrode active material is mixed with a polymeric binder compound, a solvent, a plasticizer, and optionally a conductive material into a slurry. The active material slurry is suitably agitated and then thinly applied to the substrate with a doctor blade. The substrate can be a removable substrate or a functional substrate such as a current collector (e.g., a metal mesh or mesh layer) attached to one face of the electrode film. In one embodiment, heat or radiation is applied to evaporate the solvent from the electrode film, leaving a solid residue. Heat and pressure are applied to the film to sinter it and to roll it down, thereby further densifying it. In another embodiment, the film may be air dried at a suitable temperature to provide a self-supporting film of the copolymer composition. If the substrate is removable, it is removed from the electrode film and further laminated to a current collector. With either type of substrate, the remaining plasticizer needs to be removed prior to installation into the battery.

A battery:

the battery of the present invention comprises:

(a) a first electrode comprising the active material of the present invention;

(b) a second electrode which is a counter electrode to the first electrode;

(c) an electrolyte positioned between the two electrodes.

The electrode active material of the present invention may constitute a negative electrode, a positive electrode, or both. Preferably, the electrode active material is contained in a positive electrode.

The active material of the second electrode (counter electrode) is any material compatible with the electrode active material of the present invention. Where the electrode active material comprises a positive electrode, the negative electrode may comprise any material known in the art to be compatible with the negative electrode material, including lithium, lithium alloys, such as alloys of lithium with aluminum, mercury, manganese, iron, zinc, and intercalation negative electrodes, such as those using carbon, tungsten oxide, and mixtures thereof. In a preferred embodiment, the negative electrode comprises:

(a) about 0% to about 95%, preferably about 25% to about 95%, and more preferably about 50% to about 90% of the inserted material;

(b) about 2-95% conductive material (e.g., carbon black);

In a particularly preferred embodiment, the anode comprises about 50-90% of an insertion material selected from the group consisting of active materials selected from the group consisting of metal oxides (particularly transition metal oxides), metal chalcogenides, and mixtures thereof. In another preferred embodiment, the negative electrode is free of intercalated active material, but the conductive material comprises an intercalation matrix such as carbon, graphite, coke, meso-carbon, and mixtures thereof. A preferred negative electrode intercalation material is carbon, such as coke or graphite, which is capable of forming the compound Li_xC. The inserted negative electrodes used herein are described in U.S. patent 5,700,298(Shi et al) issued on 23.12.1997, U.S. patent 5,712,059(Barker et al) issued on 27.1.1998, U.S. patent 5,830,602(Barker et al) issued on 3.11.1998, and U.S. patent 6,103,419(Saidi et al) issued on 15.8.2000, all of which are incorporated herein by reference.

In a preferred embodiment in which the electrode active material constitutes the negative electrode, the positive electrode preferably includes:

(b) about 2-95% conductive material (e.g., carbon black);

The active materials used in these positive electrodes include the electrode active material of the present invention, as well as metal oxides (particularly transition metal oxides), metal chalcogen compounds, and mixtures thereof. Other active materials include lithiated transition metal oxides, such as LiCoO₂、LiNiO₂And mixed transition metal oxides, e.g. LiCo_xNi_1-xO₂Wherein x is more than 0 and less than 1. Another preferred active material includes LiMn in a structure₂O₄Composition of (2) as an example of a lithiated spinelActive materials, and spinels surface treated as described in U.S. patent 6,183,718(Barker et al) issued 2/6/2001, which is incorporated herein by reference. Mixtures of any two or more of the above active materials may also be used. Alternatively, the positive electrode also contains a basic compound for preventing degradation of the electrode as described in U.S. patent 5,869,207 issued 2/9/1999, which is incorporated herein by reference.

The cell of the invention also comprises a suitable electrolyte which enables transport of ions between the positive and negative electrodes. Preferably, the electrolyte is a material having high ionic conductivity and having an insulating property against self-discharge during storage. The electrolyte may be a liquid or a solid. The solid electrolyte preferably comprises a polymer matrix containing an ionically conductive medium. The liquid electrolyte preferably comprises an ionically conductive liquid-forming solvent and an alkali metal salt.

One preferred embodiment is a solid polymer electrolyte comprising a solid polymer matrix formed of electrolyte-compatible materials by polymerizing organic or inorganic monomers (or their partial polymers) and which, when combined with other components of the electrolyte, results in a solid electrolyte. Suitable solid polymeric matrices include those well known in the art, and solid matrices formed from organic polymers, inorganic polymers, or monomer-forming solid matrices, as well as solid matrices formed from a portion of the polymer forming the solid matrix of monomers.

The polymer electrolyte matrix comprises a salt, typically an inorganic salt, which is uniformly dispersed in the matrix by a solvent carrier. Preferably, the solvent is a low molecular weight organic solvent added to the electrolyte, which can be used to dissolve the inorganic ionic salt. Preferably, the solvent is any compatible, relatively non-volatile, aprotic, relatively polar solvent, including dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), Ethyl Methyl Carbonate (EMC), butylene carbonate, γ -butyrolactone, triglyme, tetraglyme, lactones, esters, dimethyl sulfoxide, dioxane, sulfolane, and mixtures thereof. Preferred solvents include EC/DMC, EC/DEC, EC/DPC and EC/EMC. Preferably, the inorganic ion salt is a lithium or sodium salt, such as LiAsF₆、LiPF₆、LiClO₄、LiB(C₆H₅)₄、LiAlCl₄LiBr, andmixtures thereof, preferably less toxic salts.

The salt content is preferably about 5-65%, more preferably about 8-35%. A preferred embodiment is EC: DMC: LiPF₆In a weight ratio of about 60: 30: 10. The electrolyte compositions used herein are described in U.S. patent 5,418,091(Gozdz et al) issued at 23/5/1995, U.S. patent 5,508,130(Golovin et al) issued at 16/4/1996, U.S. patent 5,541,020(Golovin et al) issued at 30/7/1996, U.S. patent 5,620,810(Golovin et al) issued at 15/4/1997, U.S. patent 5,643,695(Barker et al) issued at 1/7/1997, U.S. patent 5,712,059(Barker et al) issued at 27/1/1997, U.S. patent 5,851,504(Barker et al) issued at 22/12/1998, U.S. patent 6,020,087(Gao) issued at 2/1/2001, and U.S. patent 6,103,419(Saidi et al) issued at 15/8/2000, all of which are incorporated herein by reference.

In addition, the electrolyte includes a separator, or is surrounded by a separator membrane. The separator allows ions to migrate through the membrane while still providing separation of charges between the two electrodes to prevent shorting. Preferably, the separator also resists temperature increases in the cell due to uncontrolled reactions, preferably by degradation at high temperatures to provide infinite resistance to prevent further uncontrolled reactions. In a preferred embodiment, the polymer matrix of the electrolyte may contain additional polymer (separator) or the original polymer matrix itself may serve as a separator, providing the desired material separation between the negative and positive electrodes.

Preferred electrolyte separator membranes comprise about two parts of polymer, based on one part of the preferred fumed silica. The conductive solvent can comprise any number of suitable solvents and salts. The ideal solvents and salts are described in 1997, 7/1U.S. Pat. No. 5,643,695(Barker et al) and U.S. Pat. No. 5,418,091(Gozdz et al), issued 5/23 in 1995, which are incorporated herein by reference. A preferred embodiment is EC: DMC: LiPF₆In a weight ratio of about 60: 30: 10.

The separator membrane element is typically a polymer, and is prepared from a composition comprising a copolymer. A preferred composition is 75-92% vinylidene fluoride and 8-25% hexafluoropropylene copolymer (available from Atochem North America under the trade name Kynar FLEX), and an organic solvent plasticizer. The copolymer composition is preferably used for the preparation of electrode film elements, since the subsequent lamination interface compatibility can be ensured. The plasticizer may be one of various organic compounds generally used as a solvent for the electrolyte salt, for example, propylene carbonate or ethylene carbonate, and a mixture of these compounds. High boiling plasticizer compounds such as dibutyl phthalate, dimethyl phthalate, diethyl phthalate and tributoxyethyl phosphate are preferred. Inorganic additives, such as fumed alumina or silanized fumed alumina, may be used to increase the physical strength and melt viscosity of the separator membrane and, in certain compositions, to increase the extent of absorption of the subsequent electrolyte solution.

Preferred cells comprise a laminate cell structure comprising a negative electrode layer, a positive electrode layer, and an electrolyte/separator between the negative and positive electrode layers. The negative and positive electrodes include a current collector. The preferred current collector is a current collecting copper foil, preferably in the form of an open mesh. The collector is connected to an external collector tab. Such structures are disclosed, for example, in U.S. patent 4,925,752(Fauteux et al) issued on 1990, 5 and 15, U.S. patent 5,011,501(Shackle et al) issued on 1991, 4 and 30, and U.S. patent 5,326,653(Chang) issued on 1994, 7 and 5, all of which are incorporated herein by reference. In one embodiment of a battery comprising a plurality of electrochemical cells, a plurality of negative tabs are preferably welded together and attached to a nickel lead. The positive electrode tabs are welded and connected to the welded leads in a similar manner, whereby the individual tabs form polarized entry points for external loads.

The lamination of the cell structure is formed by conventional methods by pressing between two metal plates at a temperature of about 120-. After lamination, the battery material storage may still contain residual plasticizer, or after extraction of the plasticizer with a selective low boiling solvent, it becomes a dry sheet storage. The plasticizer extractant is not critical and methanol or ether are typically used.

In a preferred embodiment, the electrode film comprises an electrode active material (e.g., an intercalation material such as carbon or graphite, or an intercalation compound) dispersed in a polymer binder matrix. Preferably, the electrolyte/separator membrane is a plasticized copolymer comprising a polymer separator and a suitable electrolyte for ion transport. The electrolyte/separator is disposed on the electrode element and covered with a positive electrode membrane comprising a composition of finely dispersed lithium insertion compounds in its polymer binder matrix. The installation is completed by adding a current collecting aluminum foil or a screen. A protective packaging material covers the cell and prevents the penetration of air and moisture.

In another embodiment, a multi-cell battery structure may be prepared with a copper current collector, a negative electrode, an electrolyte/separator, a positive electrode, and an aluminum current collector. The tabs of these current collector elements are the respective ends of the cell structure.

In a preferred embodiment of the lithium ion battery, the current collector layer of the aluminum foil or mesh is covered with a positive electrode film, each prepared as a layer coated with a dispersion of an intercalation electrode composition. Preferably, the intercalation compound, such as the active material of the invention, in powder form in a copolymer matrix solution is dried to form a positive electrode. An electrolyte/separator film was formed as a dry coating of a composition comprising a solution containing VdF: HFP copolymer, and then a plasticizer was coated on the positive electrode film. A negative electrode film is formed as a dry coating of powdered carbon or other negative electrode material dispersed in a matrix solution of VdF: HFP copolymer, similarly overlaid on the separator film layer. A copper current collector foil or mesh is overlaid on the negative electrode layer, completing the assembly of the cell. Thus, the VdF: HFP copolymer composition is used as an adhesive in all major battery components, positive electrode films, negative electrode films, and electrolyte/separator films. The assembled components are then heated under pressure to achieve a hot melt bond between the plasticized copolymer matrix electrode and electrolyte components and to achieve a bond with the current collector screen, thereby forming an effective battery laminate. This results in a substantially unitary and flexible cell structure.

Batteries containing electrodes, electrolytes and other materials used in the present invention are described in the following documents, all of which are incorporated herein by reference: U.S. patent 4,668,595(Yoshino et al) issued to 26.5.1987, U.S. patent 4,792,504(Schwab et al) issued to 20.12.1988, U.S. patent 4,830,939(Lee et al) issued to 16.5.5.1989, U.S. patent 4,935,317 (fautieux et al) issued to 19.6.1980, U.S. patent 4,990,413(Lee et al) issued to 5.2.5.1991, U.S. patent 5,037,712(Shackle et al) issued to 6.8.1991, U.S. patent 5,262,253(Golovin et al) issued to 16.11.1993, U.S. patent 5,300,373 (shacklel et al) issued to 5.4.5.1994, U.S. patent 5,399,447 (chalkner-Gill et al) issued to 21.1995, U.S. patent 38735 (chalner-gilner et al) issued to 5.35.1995, U.S. patent 5,411,820 (chalon.5.5.5.5.5.5.5.48325.1995), U.10 (challer et al) (chen.31-15), U.31 (challer et al) (chen. patent 1995), U.31-15 (challer et al) U.S. patent 5,482,795(Chaloner-Gill) issued on 9.1.1996, U.S. patent 5,660,948(Barker) issued on 16.9.1995, and U.S. patent 6,306,215(Larkin) issued on 23.10.2001. Preferred electrolyte matrices comprise organic polymers including VdF: HFP. Examples of using VdF: HFP for casting, laminating, and forming batteries are described in U.S. patent 5,418,091(Gozdz et al) issued at 23/5 in 1995, U.S. patent 5,460,904(Gozdz et al) issued at 24/10 in 1995, U.S. patent 5,456,00(Gozdz et al) issued at 10/10 in 1995, and U.S. patent 5,540,741(Gozdz et al) issued at 30/7 in 1996, all of which are incorporated herein by reference.

The structure of the electrochemical cell is generally determined by the electrolyte phase. Liquid electrolyte batteries generally have a cylindrical shape with a thick protective casing to prevent leakage of internal liquid. Liquid electrolyte batteries are more bulky than solid electrolyte batteries due to the liquid phase and the extended sealed casing. The solid electrolyte battery can be miniaturized and can be formed into a thin film shape. This capability allows much greater flexibility in forming the battery and constructing the receiving device. The solid polymer electrolyte battery can be formed into a flat or prismatic (rectangular) package that can be modified to accommodate the void space remaining in the electronic device during the design phase.

The following non-limiting examples illustrate the compositions and methods of the present invention.

Example 1

Comprising p-type Li_1+xNiPO₄F_xRepresentative Li₂NiPO₄The electrode active material of F was prepared as follows. First, LiNiPO was prepared according to the following reaction equation₄A precursor.

Preparation of 36.95g (0.5mol) Li using a mortar and pestle₂CO₃、164.01g(0.334mol)Ni₃(PO₄)₂·7H₂O and 44.11g (0.334mol) (NH)₄)₂HPO₄A mixture of (a). The mixture was formed into small pieces and fed into a box furnace through which ambient air was blown. The mixture was heated to a final temperature of about 800 ℃ at a ramp rate of about 2 ℃/minute and held at that temperature for 16 hours. The product was then cooled to ambient temperature (about 21 ℃).

Then, LiNiPO was used₄Preparation of Li from precursor_1+xNiPO₄F_x. In the examples where x is 1.0, the active material produced was made of the general formula Li₂NiPO₄And F represents. The material is prepared according to the following reaction equation:

when x is 1, 160.85g (1mol) of LiNiPO was prepared using a mortar and pestle₄And 25.94g (1mol) LiF. The mixture was formed into small pieces and fed into a temperature-controlled box furnace through which a stream of argon was passed. The mixture was heated to a final temperature of about 850 ℃ at a ramp rate of about 2 ℃/minute. The product was then cooled to ambient temperature (about 20 ℃).

Preparation of a catalyst containing Li₂NiPO₄A positive electrode of F electrode active material, which comprises 80% of electrode active material, 8% of Super P carbon and 12% of KYNAR^®Adhesive (KYNAR)^®Commercially available PVdF: HFP copolymer, used as the adhesive material). Making a battery comprising the positive electrode, a lithium metal negative electrode, and an electrolyte comprising 1 mole LiPF dissolved in a 2: 1 weight ratio mixture of EC and DMC₆。

Example 2

Containing Li_1+xCoPO₄F_xThe electrode active material of (3) was prepared as follows. First, LiCoPO was prepared according to the following reaction equation₄A precursor.

38.6g (0.334mol) of Li were prepared using a mortar and pestle₃PO₄And 170.29g (0.334mol) Co₃(PO₄)₂·8H₂A mixture of O. The mixture was formed into small pieces and fed into a box furnace through which ambient air was blown. The mixture was heated to a final temperature of about 800 ℃ at a ramp rate of about 2 ℃/minute and held at that temperature for about 8 hours. The product was then cooled to about 25 ℃.

Then, LiCoPO was synthesized according to the following equation₄Preparation of Li from precursor_1+xCoPO₄F_x。

When x is 1.0, the160.85g (1mol) LiCoPO were prepared with a mortar and pestle₄And 25.94g (1mol) LiF. The mixture was formed into small pieces and fed into a temperature-controlled box furnace through which a stream of argon was passed. The mixture was heated to a final temperature of about 750 ℃ at a ramp rate of about 2 ℃/minute. The product was then cooled to ambient temperature (about 21 ℃).

Example 3

Containing Li_1+xFePO₄F_xThe electrode active material of (3) was prepared as follows. First, LiFePO was prepared according to the following reaction equation₄A precursor.

103.93g (1.0mol) LiH was prepared using a mortar and pestle₂PO₄、79.86g(0.5mol)Fe₂O₃And 12.0g (1.0mol) of carbon (excess 100% by weight). The mixture was formed into small pieces and fed into a temperature-controlled box furnace through which a stream of argon was passed. The mixture was heated to a final temperature of about 750 ℃ in an inert atmosphere at a ramp rate of about 2 ℃/minute and held at that temperature for about 8 hours. The product was then cooled to room temperature (about 20 ℃).

Then, from LiFePO according to the following equation₄Preparation of Li from precursor_1+xFePO₄F_x。

When x in the formula is 1.0, 157.76g (1mol) of LiFePO was prepared using a mortar and pestle₄And 25.94g (1mol) LiF. The mixture was formed into small pieces and fed into a temperature-controlled box furnace through which a stream of argon was passed. The mixture was heated to a final temperature of about 750 ℃ at a ramp rate of about 2 ℃/minute in an inert atmosphere and held for about 8 hours. The product was then cooled to ambient temperature (about 18 ℃).

Example 4

Containing Li_1+xMnPO₄F_xThe electrode active material of (1) was prepared in the following manner, specifically taking x as an example of 1.0. First, LiM was prepared according to the following reaction equationnPO₄A precursor.

Preparation of 36.95g (0.5mol) Li using a mortar and pestle₂CO₃70.94g (1.0mol) MnO and 132.06g (1.0mol) (NH)₄)₂HPO₄A mixture of (a). The mixture was formed into small pieces and fed into a box furnace through which a stream of argon was passed. The mixture was heated to a final temperature of about 700 c at a ramp rate of about 2 c/min and held at that temperature for about 24 hours. The product was then cooled to ambient temperature.

Then, the reaction solution was prepared from LiMnPO according to the following equation₄Preparation of Li from precursor_1+xMnPO₄F_x。

When x is 1.0, 156.85g (1.0mol) of LiMnPO was prepared using a mortar and pestle₄And 25.94g (1.0mol) LiF. The mixture was formed into small pieces and fed into a temperature-controlled box furnace through which a stream of argon was passed. The mixture was heated to a final temperature of about 725 ℃ at a ramp rate of about 2 ℃/minute. The product was then cooled to ambient temperature.

Example 5

Containing Li_1+xCuPO₄F_xThe electrode active material of (3) was prepared as follows. First, LiCuPO was prepared according to the following reaction equation₄A precursor.

Preparation of 36.95g (0.5mol) Li using a mortar and pestle₂CO₃79.95g (1.0mol) CuO and 132.06g (1.0mol) (NH)₄)₂HPO₄A mixture of (a). The mixture was formed into small pieces and fed into a box furnace through which an air stream was passed. The mixture was heated to a final temperature of about 600 c at a ramp rate of about 2 c/min and held at that temperature for about 8 hours. The product was then cooled to ambient temperature.

Then theFrom LiCuPO according to the following equation₄Preparation of Li from precursor_1+xCuPO₄F_x。

When x is 1.0, 165.48g (1.0mol) of LiCuPO was prepared using a mortar and pestle₄And 25.94g (1.0mol) LiF, and the mixture was formed into chips. The mixture was placed in a covered and sealed nickel crucible and fed into a box furnace. The mixture was rapidly heated (> 50 ℃/min) to a final temperature of about 600 ℃ and held at that temperature for about 15 minutes. The product was then cooled to ambient temperature.

Example 6

Comprising the pair of general formula A_1+xM′_1-bM″_bPO₄F_xRepresentative Li₂Fe_0.9Mg_0.1PO₄Electrode active material of FThe preparation method is as follows. First, LiFe was prepared according to the following reaction equation_0.9Mg_0.1PO₄A precursor.

Preparation of 36.95g (0.5mol) Li using a mortar and pestle₂CO₃、71.86g(0.45mol)Fe₂O₃、5.83g(0.10mol)Mg(OH)₂、132.06g(1.0mol)(NH₄)₂HPO₄And 10.8g (0.90g-mol, excess 100%) of carbon. The mixture was formed into small pieces and fed into a temperature-controlled box furnace through which a stream of argon was passed. The mixture was heated to a final temperature of about 750 ℃ at a ramp rate of about 2 ℃/minute in an inert atmosphere and held at that temperature for about 8 hours. The product was then cooled to ambient temperature (about 22 ℃).

Then, from LiFe according to the following equation_0.9Mg_0.1PO₄Preparation of Li from precursor_1+xFe_0.9Mg_0.1PO₄F_xWherein x is 1.0.

Preparation of 1.082gLiFe using pot and pestle_0.9Mg_0.1PO₄And 0.181g lif. The mixture was formed into small pieces, placed in a covered and sealed nickel crucible, and fed into a temperature-controlled box furnace in an inert (argon) atmosphere. The mixture was rapidly heated to a final temperature of 700 ℃ in an inert atmosphere and held at that temperature for about 15 minutes. The product was then cooled to ambient temperature (about 21 ℃).

Example 7

Prepared from the general formula Li according to the following alternative reaction equation₂Fe_0.9Mg_0.1PO₄And F, an electrode active material.

In this example, the product of example 6 was prepared in one step from starting materials containing an alkali metal compound, two different metal sources, a phosphate compound and an alkali metal halide (exemplified by lithium fluoride). The starting materials shown in the reaction equation were mixed in molar amounts and made into small pieces. The sample was heated in an oven to a final temperature of 750 ℃ at a ramp rate of 2 ℃/minute and held at this temperature for 8 hours. At this temperature, carbon monoxide is the dominant material formed from carbon.

Example 8

Preparation of a catalyst containing the general formula Li1 according to the following alternative reaction equation_1.25Fe_0.9Mg_0.1PO₄F_0.25The electrode active material of (1).

When x is 0.25, 1.082gLiFe is premixed_0.9Mg_0.1PO₄(prepared in example 6) and 0.044g lif, and made into small pieces, fed into an oven and heated to a final temperature of 700 ℃ and held at that temperature for 15 minutes. The sample was cooled and removed from the furnace. Little weight loss was recorded in the reaction, withLithium fluoride is totally added into a phosphate structure to prepare the lithium fluoride with the general formula of Li_1.25Fe_0.9Mg_0.1PO₄F_0.25The active materials are shown to be uniform.

Example 9

Containing Na_1.2VPO₄F_1.2The electrode active material of (3) was prepared as follows. In the first step, the metal phosphate is prepared by carbothermic reduction of a metal oxide, here exemplified by vanadium pentoxide. The overall reaction equation for carbothermic reduction is as follows.

Using 31.5g of VPO₅、39.35gNH₄H₂PO₄And 4.5g carbon (10% excess). Each precursor was premixed using a bowl and pestle, and then made into small pieces. The chips were fed into an oven through which a flowing air atmosphere was passed. The sample was heated to a final temperature of 300 c at a ramp rate of 2 c/min and held at that temperature for 3 hours. The sample was cooled to room temperature, removed from the furnace, recovered, mixed again and formed into small pieces again. The chips were fed into a furnace with an argon atmosphere. The sample was heated to a final temperature of 750 ℃ at a ramp rate of 2 ℃/minute and held at this temperature for 8 hours.

In the second step, the vanadium phosphate produced in the first step is reacted with an alkali metal halide (exemplified by sodium fluoride) according to the following reaction equation.

xNaF+VPO₄→Na_xVPO₄F_x

Using 5.836gVPO₄And 1.679 gNaF. The precursor was premixed using a bowl and pestle and then made into small pieces. The chips were fed into a furnace through which a flowing argon atmosphere was passed, and the samples were heated to a final temperature of 750 ℃ at a temperature ramp rate of 2 ℃/minute and held at that temperature for 1 hour. The sample was cooled to room temperature and removed from the furnace.

To prepare Na_1.2VPO₄F_1.2Repeated with an excess of 20% by weight of sodium fluoride over the previous reactionAnd (4) reacting. The precursor was premixed with a bowl and pestle as before. The sample was heated to a final temperature of 700 ℃ and held at this temperature for 15 minutes. The sample was cooled to room temperature and removed from the furnace. There is only a small weight loss during the reaction,this indicates that almost all of the NaF was involved in the reaction.

To prepare a compound represented by the general formula Na_1.2VPO₄F_1.2The active material represented was repeatedly reacted with an excess of about 50 mass% of sodium fluoride over the first reaction. The sample was heated at 700 ℃ for 15 minutes, cooled, and removed from the furnace.

Example 10

Comprising as formula A_xMPO₄Z_xExample (2) Na_xCrPO₄F_xThe electrode active material of the compound represented was prepared according to the following reaction equation.

The starting materials were mixed and made into small pieces using a mortar and pestle, placed in an oven and heated to 800 ℃, and held at that temperature for 6 hours.

Example 11

Preparation of a catalyst containing NaMnPO according to the following reaction equation₄And F.

For this reaction, MnPO₄Can be reduced from Mn by carbothermic reduction₂O₅Is convenient for preparation. Mix 1.87gMnPO₄·2H₂O and 0.419g naf, were formed into small pieces and placed in an oven to be heated to a final temperature of 500 c, and held at that temperature for 15 minutes.

Example 12

Preparation of a catalyst comprising NaCoPO according to the following reaction equation₄And F.

0.33Co₃O₄+NH₄H₂PO₄+NaF+0.08₃O₂→NaCoPO₄F+NH₃+1.5H₂O

The active material is prepared under oxidizing conditions, wherein the metal in the final product has a higher oxidation state than the metal in the starting material. Mixing 3gCo₃O₄1.57gNaF and 4.31gNH₄H₂PO₄Pellets were formed and heated to a final temperature of 300 c and held at that temperature for 3 hours. The sample was cooled, removed from the furnace, re-formed into small pieces, and heated back to a final temperature of 800 c and held at that temperature for 8 hours.

Example 13

Preparation of a catalyst containing Li according to the following reaction equation_0.1Na_0.9VPO₄And F.

As an alternative to the use of alkaline fluorides, VPO may also be used₄And NH₄Reaction between F, and Li₂CO₃And Na₂CO₃A mixture of (a).

To prepare Li_0.1Na_0.9VPO₄F, premix 1.459gVPO₄0.026g lif and 0.378g naf, made into small pieces and placed in a furnace heated to a final temperature of 700 ℃. The temperature was maintained for 15 minutes, after which the sample was cooled to room temperature and removed from the furnace. To prepare Li_0.95Na_0.05VPO₄F, premix 1.459gVPO₄0.246g LiF and 0.021g NaF, and heating in an oven according to the previous steps.

Example 14

Hydrothermal preparation of a catalyst containing NaVPO according to the following reaction equation₄And F.

Pre-mix 1.49g VPO with about 20ml deionized water₄And 1.42g NaF, were formed into small pieces, fed into and sealed in a Parr model 4744 acid digestion vesselIs a Teflon lined stainless steel hydrothermal reaction vessel. The vessel was placed in a furnace and heated at a ramp rate of 5 deg.c/min to a final temperature of 250 deg.c to generate an internal pressure, and held at that temperature for 48 hours. The sample was slowly cooled to room temperature and removed from the oven for analysis. The product sample was repeatedly washed with deionized water to remove unreacted impurities. The sample was then dried in an oven with a flow of argon at 250 c for one hour.

Example 15

Prepared from the general formula NaVPO according to the reaction equation available below₄An electrode active material represented by OH.

In this example, the reaction of example 14 was repeated except that the appropriate molar amount of sodium hydroxide was used in place of sodium fluoride. The reaction described in example 14 was carried out hydrothermally. Hydroxyl groups are added to the active material at a lower reaction temperature.

Example 16

Preparation of a catalyst comprising NaVPO according to the following reaction equation₄And F.

Pre-mix 1.23g VPO with about 20ml deionized water₄、0.31gNH₄F and 0.45gNa₂CO₃Fed into and sealed in a Parr model 4744 acid digestion vessel, which is a Teflon lined reaction vessel. Will be heldThe vessel was placed in an oven, heated to a final temperature of 250 ℃ and held at this temperature for 48 hours. The sample was cooled to room temperature and removed for analysis. The sample was repeatedly washed with deionized water to remove unreacted impurities, and then dried under an argon atmosphere at 250 ℃ for one hour.

Example 17

Prepared from the general formula A according to the following reaction equation_aM_b(PO₄)₃Z_dContaining Li₄Fe₂(PO₄)₃And F.

Here, M₂O₃Represents a +3 metal oxide or a mixture of +3 metal oxides. Substitution of 2Li₂CO₃Similar compounds having lithium, sodium and potassium as alkali metals can be prepared using a mixture of lithium carbonate, sodium carbonate and potassium carbonate totaling 2 moles. The starting materials alkali metal carbonate, the oxide in the +3 oxidation state of the metal or mixed metal, ammonium dihydrogen phosphate and ammonium fluoride are combined in stoichiometric ratios expressed in powdered form and the powders are mixed and made into tablets as described in the previous examples. The chips were fed into an oven and heated to a final temperature of about 800 c, at which temperature they were held for 8 hours. The reaction mixture was then cooled and removed from the furnace.

Example 18

Preparation of a catalyst containing Na according to the following reaction equation₂Li₂M₂(PO₄)₃And F.

The starting materials were mixed in the stoichiometric ratios indicated and reacted according to the general procedure of example 17. Here, MPO₄Represents a metal +3 phosphate or a mixture of metal +3 phosphates.

Example 19

Comprising the pair of general formula A_aM_b(PO₄)₃Z_dRepresentative Li₄V₂(PO₄)₃The electrode active material of the active material of F was synthesized by carbothermic method according to the following reaction equation. The reaction is based on the conversion of carbon to carbon monoxide by a carbothermic reduction mechanism.

In this reaction equation, carbon is supplied in excess, so that the products formed are limited by other starting materials. The starting materials were mixed, formed into small pieces and heated according to the method described in example 7.

Example 20

Preparation of a catalyst containing Li5Mn according to the following reaction equation₂(PO₄)₃F₂The electrode active material of (1).

The starting materials were mixed in the stoichiometric ratios indicated and reacted under conditions analogous to those of examples 17-18. This reaction represents the addition of a metal in the +4 oxidation state to the active material of the present invention containing 3 phosphate groups. The reaction proceeds without reduction.

Example 21

Synthesis of a catalyst containing Li according to the following equation₆V₂(PO₄)₃And F.

The equation assumes that the carbothermic reduction reaction is accompanied by the production of carbon monoxide. Here again, a carbon excess is supplied, in which case the vanadium +5 species are reduced until the lowest oxidation state +2. It will be appreciated that such reduction is possible in the reaction, since there is sufficient lithium in the reaction to neutralize the active material (PO)₄)₃F^-10The amount of groups goes into the reaction product.

Example 22

Preparation of a catalyst containing Li_1.5Na_1.5M₂(PO₄)₂(PO₃F) F, wherein the phosphate group is partially substituted with a mono-fluoro monophosphate. The process was similar to that described in example 18, except that LiHPO was used₃F replacing NH₄H₂PO₄And (c) other than. The active material is prepared by the following reaction equation:

the starting materials are provided in the molar ratios indicated. The powdered starting materials are mixed, formed into small pieces, and placed in an oven at about 700 ℃ for 1-8 hours.

In another embodiment, additional molar amounts of fluoride are provided such that the reaction proceeds according to the following equation:

this example shows the partial substitution of phosphate with monofluorophosphate, and the control of the reaction product by selecting the molar amount of starting material.

Example 23

Na-containing synthesis according to the following equation_0.2LiCr(PO₄)_0.8(SiO₄)_0.2And F.

The starting materials were provided in powder form in the indicated molar amounts, mixed, made into small pieces and placed in an oven. The sample was heated to a final temperature of 750 ℃ and held at this temperature for 4 hours.

Example 24

Comprising the pair of general formula A_nM1_y ⁺³M2_2-y ⁺³(PO₄)_z(SbO₄)_3-zF (wherein A is Li, n is 4, M1 is Al, M2 is V, M3 is Mg, y is 1, and z is 2.5) represents Li₄AlV(PO₄)_2.5(SbO₄)_0.5The electrode active material of F is according to the following reaction equation.

Example 25

Containing Li_2.025Co_0.9Al_0.025Mg_0.05PO₄The electrode active material of F was prepared as follows (this example shows thatSynthesis of mixed metal active materials with lithium and three different metals, two of which are in the +2 oxidation state and one of which is in the +3 oxidation state). A is Li, a is 2.025, M1 is Co, M2 is Al, and M3 is Mg, the reaction being carried out according to the following equation.

The starting materials were provided in powder form in the indicated molar amounts, mixed, formed into small pieces and placed in an oven at 750 ℃ for 4 hours to produce the reaction product.

The examples and other embodiments described herein are exemplary only and are not intended to limit the full scope of the compositions and methods of the present invention. Equivalent changes, modifications and variations of the specific embodiments, materials, compositions and methods of the invention may be made within the scope of the invention, with similar results.

Claims

1. An electrode active material which is a compound having the following general formula:

A_aM_b(XY₄)_cZ_d

in the formula

(b) m is one or more metals, including at least one metal capable of being oxidized to a higher valence state, and 1. ltoreq. b.ltoreq.3;

wherein M, X, Y, Z, a, b, c, d, X and Y are selected to maintain the electroneutrality of the compound.

2. The electrode active material according to claim 1, wherein: wherein c is 1.

3. The electrode active material according to claim 2, wherein: in the formula, a is more than or equal to 0.1 and less than or equal to 3, and d is more than or equal to 0.1 and less than or equal to 3.

4. The electrode active material according to claim 3, wherein: in the formula, a is more than or equal to 1 and less than or equal to 3, and d is more than or equal to 1 and less than or equal to 3.

5. The electrode active material according to claim 2, wherein: the active material has an olivine structure.

6. The electrode active material according to claim 1, wherein: wherein c is 3.

7. The electrode active material according to claim 6, wherein: in the formula, a is more than or equal to 2 and less than or equal to 6, and d is more than or equal to 2 and less than or equal to 6.

8. The electrode active material according to claim 7, wherein: in the formula, a is more than or equal to 3 and less than or equal to 6, and d is more than or equal to 3 and less than or equal to 6.

9. The electrode active material according to claim 6, wherein: the active material has a NASICON structure.

10. The electrode active material according to claim 1, wherein: wherein A is Li.

11. The electrode active material according to claim 1, wherein: wherein A is selected from Na, K and mixtures thereof, and mixtures thereof with Li.

12. The electrode active material according to claim 11, wherein: wherein A is Na.

13. The electrode active material according to claim 1, wherein: wherein M comprises two or more transition metals selected from groups 4 to 11 of the periodic Table of the elements.

14. The electrode active material according to claim 13, wherein: the transition metal is selected from Fe, Co, Ni, Mn, Cu, V, Zr, Ti and Cr.

15. The electrode active material according to claim 1, wherein: m is M 'M ", wherein M' is at least one transition metal selected from groups 4 to 11 of the periodic Table of the elements; m' is at least one element selected from groups 2, 3, 12, 13 or 14 of the periodic Table of the elements.

16. The electrode active material according to claim 15, wherein: wherein M' is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

17. The electrode active material according to claim 16, wherein: wherein M' is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof.

18. The electrode active material according to claim 15, wherein: wherein M' is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al and mixtures thereof.

19. The electrode active material according to claim 18, wherein: wherein M' is selected from the group consisting of Mg, Ca, Zn, Ba, Al and mixtures thereof.

20. The electrode active material according to claim 1, wherein: wherein X' comprises As, Sb, Si, Ge, S and mixtures thereof; x' comprises As, Sb, Si, Ge and mixtures thereof.

21. The electrode active material according to claim 20, wherein: wherein X' is Si; x' is Si.

22. The electrode active material according to claim 1, wherein: XY₄Selected from X' O_4-xY′_x、X′O_4-yY′_2y、X″S₄And mixtures thereof, wherein X 'is P, X' is P, 0 < X < 3, 0 < y < 4.

23. The electrode active material according to claim 1, wherein: XY₄Selected from X' O_4-xY′_x、X′O_4-yY′_2y、X″S₄And mixtures thereof, wherein X' is P, As, Sb, Si, Ge, S and mixtures thereof; x' is P, As, Sb, Si, Ge and mixtures thereof; y' is halogen; x is more than 0 and less than 3, and y is more than 0 and less than 4.

24. The electrode active material according to claim 1, wherein: wherein Y' is F.

25. The electrode active material according to claim 1, wherein: in the formula XY₄Is X' S₄。

26. The electrode active material according to claim 1, wherein: wherein Z comprises F.

27. The electrode active material according to claim 1, wherein: wherein Z is F.

28. The electrode active material according to claim 27, wherein: XY₄Selected from X' O_4-xY′_x、X′O_4-yY′_2y、X″S₄And mixtures thereof, wherein X 'is P, X' is P, 0 < X < 3, 0＜y＜4。

29. The electrode active material according to claim 1, wherein: wherein Z is OH.

30. The electrode active material of claim 29, wherein: wherein X 'is P and X' is P.

31. The electrode active material according to claim 1, wherein: wherein X is Br or Cl.

32. The electrode active material of claim 31, wherein: wherein X 'is P and X' is P.

33. An electrode active material which is a compound having the following general formula:

Li_aM_b(PO₄)Z_d

in the formula

(a)0.1＜a≤4；

(c) z is halogen, and d is more than 0.1 and less than or equal to 4;

34. The electrode active material according to claim 33, wherein: wherein M' is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

35. The electrode active material of claim 34, wherein: wherein M' is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof.

36. The electrode active material according to claim 33, wherein: wherein M' is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al and mixtures thereof.

37. The electrode active material of claim 36, wherein: wherein M' is selected from the group consisting of Mg, Ca, Zn, Ba, Al and mixtures thereof.

38. The electrode active material according to claim 33, wherein: wherein Z is F.

39. An electrode active material which is a compound having the following general formula:

Li_aM_b(PO₄)Z_d

in the formula

(a)0.1＜a≤4；

40. The electrode active material of claim 37, wherein: m is M 'M ", wherein M' is at least one transition metal selected from groups 4 to 11 of the periodic Table of the elements; m' is at least one element selected from groups 2, 3, 12, 13 or 14 of the periodic Table of the elements.

41. The electrode active material of claim 40, wherein: wherein M' is selected from the group consisting of Fe, Co, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

42. The electrode active material of claim 41, wherein: wherein M' is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof.

43. The electrode active material of claim 40, wherein: wherein M' is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al and mixtures thereof.

44. The electrode active material of claim 43, wherein: wherein M' is selected from the group consisting of Mg, Ca, Zn, Ba, Al and mixtures thereof.

45. An electrode active material which is a compound having the following general formula:

Li₂M(PO₄)Z_d

in the formula

(c) z is halogen, d is more than 0.1 and less than or equal to 2;

46. The electrode active material of claim 45, wherein: wherein M' is selected from the group consisting of Fe, Co, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

47. An electrode active material according to claim 46, wherein: wherein M' is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof.

48. The electrode active material of claim 45, wherein: wherein M' is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al and mixtures thereof.

49. The electrode active material of claim 48, wherein: wherein M' is selected from the group consisting of Mg, Ca, Zn, Ba, Al and mixtures thereof.

50. The electrode active material of claim 45, wherein: wherein Z is F.

51. The electrode active material of claim 45, wherein: in the general formula Li₂MPO₄In F, M is selected from Ti, V, Cr, Mn, Fe, Co, Cu, Zn or their mixture.

52. An electrode active material according to claim 51, wherein: wherein M is Fe, Co, Mn or their mixture.

53. The electrode active material of claim 52, wherein: the general formula is Li₂CoPO₄F or Li₂FePO₄F。

54. The electrode active material of claim 45, wherein: wherein M 'is Fe or Co, M' is Mg, and X is F.

55. The electrode active material of claim 54, wherein: wherein M' is Fe.

56. The electrode active material of claim 55, wherein: the general formula is Li₂Fe_0.9Mg_0.1PO₄F。

57. An electrode active material which is a compound having the following general formula:

A_aM_b(XY₄)₃Z_d

in the formula

(a) A is selected from Li, Na, K and their mixture, 2 ≤ a ≤ 8;

(c)XY₄selected from X' O_4-xY′_x、X′O_4-yY′_2y、X″S₄And mixtures thereofCompounds of formula wherein X' is P, As, Sb, Si, Ge, S and mixtures thereof; x' is P, As, Sb, Si, Ge and mixtures thereof; y' is halogen; x is more than or equal to 0 and less than 3; y is more than 0 and less than 4;

58. The electrode active material of claim 57, wherein: wherein A is Li.

59. The electrode active material of claim 57, wherein: wherein A is Na, K or their mixture.

60. The electrode active material of claim 57, wherein: wherein M comprises two or more transition metals selected from groups 4 to 11 of the periodic Table of the elements.

61. The electrode active material of claim 60, wherein: the transition metal is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

62. The electrode active material of claim 57, wherein: m is M 'M ", wherein M' is at least one transition metal selected from groups 4 to 11 of the periodic Table of the elements; m' is at least one element selected from groups 2, 3, 12, 13 or 14 of the periodic Table of the elements.

63. The electrode active material of claim 62, wherein: wherein M' is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

64. An electrode active material according to claim 63, wherein: wherein M' is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof.

65. The electrode active material of claim 62, wherein: wherein M' is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al and mixtures thereof.

66. An electrode active material according to claim 65, wherein: wherein M' is selected from the group consisting of Mg, Ca, Zn, Ba, Al and mixtures thereof.

67. The electrode active material of claim 57, wherein: in the formula XY₄Is PO₄。

68. The electrode active material of claim 57, wherein: wherein X' comprises As, Sb, Si, Ge, S and mixtures thereof; x' comprises As, Sb, Si, Ge and mixtures thereof; x is more than 0 and less than 3.

69. The electrode active material of claim 57, wherein: wherein Z is F.

70. The electrode active material of claim 57, wherein: wherein Z is OH.

71. An electrode active material which is a compound having the following general formula:

A_aM_b(XY₄)₂Z_d

in the formula

(a) A is selected from Li, Na, K and their mixture, and 0.1 < a.ltoreq.6;

(c)XY₄selected from X' O_4-xY′_x、X′O_4-yY′_2y、X″S₄And mixtures thereof, wherein X' is P, As, Sb, Si, Ge, S and mixtures thereof; x' is P,As, Sb, Si, Ge and mixtures thereof; y' is halogen; x is more than or equal to 0 and less than 3; y is more than 0 and less than 4;

72. The electrode active material of claim 71, wherein: wherein A is Li.

73. The electrode active material of claim 71, wherein: wherein A is Na, K or their mixture.

74. The electrode active material of claim 71, wherein: wherein M comprises two or more transition metals selected from groups 4 to 11 of the periodic Table of the elements.

75. The electrode active material of claim 74, wherein: the transition metal is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

76. The electrode active material of claim 71, wherein: m is M 'M ", wherein M' is at least one transition metal selected from groups 4 to 11 of the periodic Table of the elements; m' is at least one element selected from groups 2, 3, 12, 13 or 14 of the periodic Table of the elements.

77. An electrode active material according to claim 76, wherein: wherein M' is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

78. An electrode active material according to claim 77, wherein: wherein M' is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof.

79. An electrode active material according to claim 76, wherein: wherein M' is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al and mixtures thereof.

80. An electrode active material according to claim 79, wherein: wherein M' is selected from the group consisting of Mg, Ca, Zn, Ba, Al and mixtures thereof.

81. The electrode active material of claim 71, wherein: in the formula XY₄Is PO₄。

82. The electrode active material of claim 71, wherein: wherein X' comprises As, Sb, Si, Ge, S and mixtures thereof; x' comprises As, Sb, Si, Ge and mixtures thereof; x is more than 0 and less than 3.

83. The electrode active material of claim 71, wherein: wherein Z is F.

84. The electrode active material of claim 71, wherein: wherein Z is OH.

85. An electrode comprising a binder, a conductive carbonaceous material, and the active material of claim 1.

86. An electrode comprising a binder, a conductive carbonaceous material, and the active material of claim 33.

87. An electrode comprising a binder, a conductive carbonaceous material, and the active material of claim 39.

88. An electrode comprising a binder, a conductive carbonaceous material, and the active material of claim 45.

89. An electrode comprising a binder, a conductive carbonaceous material, and the active material of claim 57.

90. An electrode comprising a binder, a conductive carbonaceous material, and the active material of claim 71.

91. A lithium battery, comprising:

(a) a first electrode comprising the active material of claim 1;

(b) a second electrode as a counter electrode to the first electrode;

(c) an electrolyte positioned between the two electrodes.

92. A lithium battery as claimed in claim 91, wherein: the first electrode is a positive electrode and the second electrode is an intervening negative electrode.

93. A lithium battery as in claim 92, wherein: the second electrode comprises a metal oxide, a metal sulfide, carbon, graphite, and mixtures thereof.

94. A lithium battery, comprising:

(a) a first electrode comprising the active material of claim 33;

(b) a second electrode as a counter electrode to the first electrode;

(c) an electrolyte positioned between the two electrodes.

95. A lithium battery, comprising:

(a) a first electrode comprising the active material of claim 39;

(b) a second electrode as a counter electrode to the first electrode;

(c) an electrolyte positioned between the two electrodes.

96. A lithium battery, comprising:

(a) a first electrode comprising the active material of claim 45;

(b) a second electrode as a counter electrode to the first electrode;

(c) an electrolyte positioned between the two electrodes.

97. A lithium battery, comprising:

(a) a first electrode comprising the active material of claim 57;

(b) a second electrode as a counter electrode to the first electrode;

(c) an electrolyte positioned between the two electrodes.

98. A lithium battery as in claim 97, wherein: the first electrode is a positive electrode and the second electrode is an intervening negative electrode.

99. A lithium battery as in claim 98, wherein: the second electrode comprises a metal oxide, a metal sulfide, carbon, graphite, and mixtures thereof.

100. A lithium battery, comprising:

(a) a first electrode comprising the active material of claim 71;

(b) a second electrode as a counter electrode to the first electrode;

(c) an electrolyte positioned between the two electrodes.